JPH08248601A - Color development main chemical, processing composition, and color image formation - Google Patents

Abstract

PURPOSE: To provide an adequate quick processing, a low fogging photographic density, and an excellent image in image fastness by using a specified color development chemical. CONSTITUTION: A color development chemical is expressed by a formula. In the formula, r<1> , R<2> represent alkyl groups, and R<3> represents a substitutional group. (n) represents integers of 0 to 2. Z represents a nonmetal atom group forming an aromatic ring of five members or six members containing one - three carbon atoms. Image exposed silver halide color photographic sensitized material is developed by processing liquid containing at least one kind of color development main chemical. Quick processing is thereby possible, a fogging photographic density is low, and color balance is excellent in three colors of yellow, magenta, and cyan. Sensitivity and gradation change in a running process is little, and effect on photographic performance becomes little even in a state that halogen ions (particularly, chlorine ions and bromine ions) are accumulated.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel silver halide color photographic developing agent, a processing composition containing the developing agent and a color image forming method using the processing solution. The present invention relates to a color photographic developing agent which is suitable for rapid processing and is capable of obtaining an image with less fog, and has excellent fastness of the obtained image, a processing composition containing the developing agent, and a color image forming method using the processing solution. It is a thing.

[0002]

2. Description of the Related Art In recent years, due to an increase in in-store processing called minilabs and an increase in the amount of color negative film used in the field of news photography, development processing can be completed in a shorter time, and prints can be immediately provided to customers or newspapers. There is a rapid increase in the demand for publication in the etc. In particular, regarding the processing of a color negative film, which requires a longer time than that of a color paper, there is a particularly high demand for shortening the processing time. In a color photographic light-sensitive material mainly composed of silver iodobromide emulsion such as a color negative film, the processing time can be shortened by changing the color developing agent. For example, JP-A-5-113635 and JP-A-53-69035
No. 2 of US Pat. No. 2,304,953.
It was found that 4-dialkylaminoanilines having an alkoxy group at the position contribute to shortening the treatment time. Further, 6-amino-1,2,3,4-tetrahydroquinolines and 5-amino-2,3-dihydroindoles described in JP-A-4-45440 also contribute to shortening the treatment time. I understood.

However, when a color photographic light-sensitive material mainly containing a silver iodobromide emulsion was developed with the compounds described in these specifications, it was found to have some drawbacks. Since the image density of the unexposed area is high, that is, the fog is large, and the image density of yellow and cyan in the exposed area is not sufficient compared to magenta, the color balance of the three colors is poor. Also, the fastness of the obtained image was not sufficient.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to have suitability for rapid processing, low fog density, and low yellow and cyan image densities. Another object is to provide a color developing agent that is sufficient and has excellent image fastness, and to provide a processing solution for a silver halide color photographic light-sensitive material and a color image forming method using the developing agent.

[0005]

Means for Solving the Problems The above-mentioned problems are (1) a color developing agent represented by the following general formula (D). General formula (D)

[0006]

Embedded image

In the formula, R ¹ and R ² represent an alkyl group,
R ³ represents a substituent. n represents an integer of 0 to 2. Z
Represents a group of non-metal atoms forming a 5- or 6-membered aromatic ring containing 1 to 3 carbon atoms. (2) A color photographic processing composition comprising at least one of the color developing agents described in (1) above. (3) A color image forming method, which comprises developing an image-exposed silver halide color photographic light-sensitive material with a processing solution containing at least one of the color developing agents described in (1) above. It was solved by (1) to (3) above.

JP-A-5-113635 and JP-A-53-153
The alkoxy developing agents specifically described in U.S. Pat. No. 6,903,529 and U.S. Pat. No. 2,304,953 have rapidity but have poor color balance of three colors and large fog. Further, it worsens with the tetrahydroquinoline type and dihydroindole type developing agents described in JP-A-4-45440. As a result of diligent studies on the developing agent represented by the general formula (D), it has been found that the developing agent has the same rapidity as the alkoxy developing agent and the defect of the alkoxy developing agent can be greatly improved. .

The advantages of the color image forming method using the color developing agent represented by the general formula (D) are that rapid processing is possible, fog density is low, and three colors of yellow, magenta and cyan are used in rapid processing. Excellent balance, small change in sensitivity and gradation in running processing, small influence on photographic properties even when halogen ions (especially chlorine ion, bromine ion) are accumulated,
The obtained image has excellent fastness.

In the present invention, Z of the compound represented by the general formula (D) forms an aromatic ring. When Z does not form an aromatic ring, it may not exhibit developing activity as a color developing agent.

In the present invention, R ¹ , R ² , R ³ , n and Z in the compound represented by the general formula (D) will be described in detail below.

R ¹ and R ² each have 1 to 1 carbon atoms which may be substituted.
Represents 5, preferably 1 to 8, straight chain, branched chain or cyclic alkyl groups. Examples of alkyl groups include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, isopropyl, 1-methylpropyl, isobutyl, t-butyl, 1-ethyl. Propyl, 2-methylbutyl, isopentyl, 2-ethylhexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, preferably methyl, ethyl, n-propyl, isopropyl, isobutyl, t-butyl, n-pentyl, n-hexyl. . More preferably, methyl, ethyl, n-propyl,
Isopropyl and n-butyl. Examples of the substituent include a hydroxy group, a halogen atom (for example, a fluorine atom,
Chlorine atom), an aryl group (preferably having 6 to 7 carbon atoms, for example, phenyl, m-hydroxyphenyl), a heterocyclic group (having at least one oxygen atom, nitrogen atom, or sulfur atom having 1 to 5 carbon atoms) 5 A 6-membered or 6-membered saturated or unsaturated heterocycle, for example, 2-furyl, 2-thienyl, 2-pyrimidinyl, imidazolyl, pyrazolyl), an alkoxy group (preferably having 1 to 7 carbon atoms, for example, methoxy, Ethoxy, 2-hydroxyethoxy, 2
-Methanesulfonylethoxy), an aryloxy group (preferably having 6 to 7 carbon atoms, for example, phenoxy, p-hydroxyphenoxy), an acylamino group (preferably having 1 to 7 carbon atoms, for example, acetamide, 2-methoxypropionamide, p-hydroxybenzoylamide), an alkylamino group (preferably having 1 to 7 carbon atoms, for example, dimethylamino, diethylamino, 2-hydroxyethylamino), an anilino group (preferably having 6 to 7 carbon atoms, for example, anilino, m- Nitroanilino, m-hydroxyanilino), ureido group (preferably having 1 to 7 carbon atoms, for example, ureido, methylureido, N, N-diethylureido, 2-methanesulfonamidoethylureido), sulfamoylamino group (carbon The number 0 to 7 is preferable, for example, dimethylsulf Moylamino, methylsulfamoylamino, 2-methoxyethylsulfamoylamino), alkylthio group (preferably having 1 to 7 carbon atoms, for example, methylthio, ethylthio, benzylthio), arylthio group (preferably having 6 to 7 carbon atoms, for example, , Phenylthio, 2-carboxyphenylthio, 4-hydroxyphenylthio), alkoxycarbonylamino group (preferably having 2 to 7 carbon atoms, for example, methoxycarbonylamino, ethoxycarbonylamino, 3-methanesulfonylpropoxycarbonylamino), sulfonylamino. Group (preferably having 1 to 7 carbon atoms, for example, methanesulfonamide, p-toluenesulfonamide, 2-methoxyethanesulfonamide), carbamoyl group (preferably having 1 to 7 carbon atoms, for example, carbamoyl, N, N- Methylcarbamoyl, N-ethylcarbamoyl), sulfamoyl group (preferably having 0 to 7 carbon atoms, for example, sulfamoyl, dimethylsulfamoyl, ethylsulfamoyl), sulfonyl group (preferably aliphatic or carbon having 1 to 5 carbon atoms) An aromatic sulfonyl group of the formula 6 to 7, for example, methanesulfonyl, ethanesulfonyl, 2-chloroethanesulfonyl), an alkoxycarbonyl group (preferably having 1 to 7 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl). ), A heterocyclic oxy group (a 5-membered or 6-membered saturated or unsaturated heterocyclic oxy group having at least one oxygen atom, nitrogen atom, or sulfur atom having 1 to 5 carbon atoms, which constitutes a ring) The number of heteroatoms and the kind of element may be one or plural, for example, 1- Phenyltetrazolyl-5-oxy, 2
-Tetrahydropyranyloxy, 2-pyridyloxy), azo group (preferably having 1 to 7 carbon atoms, for example, phenylazo, 2-hydroxyphenylazo, 4-sulfophenylazo), acyloxy group (preferably having 1 to 7 carbon atoms) , For example, acetoxy, benzoyloxy, 4-hydroxybutanoyloxy, carbamoyloxy group (preferably having 1 to 7 carbon atoms, for example, N, N-dimethylcarbamoyloxy, N-methylcarbamoyloxy, N-
Phenylcarbamoyloxy), silyl group (C3-C3)
7 are preferable, for example, trimethylsilyl, isopropyldiethylsilyl, t-butyldimethylsilyl), silyloxy group (preferably having 3 to 7 carbon atoms, for example, trimethylsilyloxy, triethylsilyloxy), aryloxycarbonylamino group (having 7 carbon atoms). Preferably, for example, phenoxycarbonylamino, 4-hydroxyphenoxycarbonylamino), an imide group (having 4 to 7 carbon atoms)
Is preferred, for example, N-succinimide), a heterocyclic thio group (a 5- or 6-membered saturated or unsaturated heterocyclic thio group containing at least one oxygen atom, nitrogen atom, or sulfur atom having 1 to 5 carbon atoms). The number of hetero atoms constituting the ring which is a group and the number of elements may be one or more, for example, 2-benzothiazolylthio, 2-pyridylthio), sulfinyl group (preferably having 1 to 7 carbon atoms, For example, methanesulfinyl, benzenesulfinyl, ethanesulfinyl), phosphonyl group (preferably having 2 to 7 carbon atoms, for example, methoxyphosphonyl, ethoxyphosphonyl, phenoxyphosphonyl), aryloxycarbonyl group (preferably having 7 carbon atoms, for example, , Phenoxycarbonyl, 3-hydroxyphenoxycarbonyl), acyl groups (preferably having 1 to 7 carbon atoms). Properly, for example, acetyl, benzoyl, 4-hydroxybenzoyl).

Preferred examples of the substituent include a hydroxy group, aryl group, carboxy group, sulfo group, acylamino group, ureido group, sulfamoylamino group, sulfonylamino group, carbamoyl group and sulfamoyl group. More preferable examples are a hydroxy group, a carboxy group, a sulfo group, a sulfonylamino group, a carbamoyl group and a sulfamoyl group.

R ¹ and R ² are preferably, for example, methyl, ethyl, n-propyl, isopropyl, t-butyl, n-pentyl, benzyl, 2-hydroxyethyl,
3-hydroxypropyl, 4-hydroxybutyl, 5-
Hydroxypentyl, 6-hydroxyhexyl, 2,3
-Dihydroxypropyl, 3,4-dihydroxybutyl, 2-methanesulfonamidoethyl, 3-methanesulfonamidopropyl, 2-methanesulfonylethyl, 2
-Methoxyethyl, 2-acetamidoethyl, 2-carbamoylethyl, 3-carbamoylpropyl, 4-carbamoylbutyl, 2-carbamoyl-1-methylethyl, 2-carboxyethyl, 3-carboxypropyl,
4-carboxybutyl, 2-sulfoethyl, 4-sulfobutyl, 2-sulfamoylethyl, 3-sulfamoylpropyl, 4-sulfamoylbutyl, 2-ureidoethyl, 3-ureidopropyl, 2-sulfamoylamino It is ethyl. More preferably, methyl, ethyl,
n-propyl, 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 2,3-dihydroxypropyl, 3,4-dihydroxybutyl, 2-methanesulfonamidoethyl, 2-carboxyethyl, 4-sulfobutyl, 2 -Ureidoethyl, 2-carbamoylethyl, 2-sulfamoylethyl, 2-sulfamoylaminoethyl.

R ³ represents a substituent, and in this case, the substituent has 1 to 15 carbon atoms which may be substituted, preferably 1 to
Eight straight, branched or cyclic alkyl groups and R ¹ , R
It is synonymous with the substituent explained in ² .

R ³ is preferably, for example, methyl,
Ethyl, n-propyl, isopropyl, t-butyl, n
-Pentyl, benzyl, 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 5-hydroxypentyl, 6-hydroxyhexyl, 2,3-dihydroxypropyl, 3,4-dihydroxybutyl, 2-
Methanesulfonamidoethyl, 3-methanesulfonamidopropyl, 2-methanesulfonylethyl, 2-methoxyethyl, 2-acetamidoethyl, 2-carbamoylethyl, 3-carbamoylpropyl, 4-carbamoylbutyl, 2-carbamoyl-1-methyl Ethyl, 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, 2-sulfoethyl, 4-sulfobutyl, 2
-Sulfamoylethyl, 3-sulfamoylpropyl, 4-sulfamoylbutyl, 2-ureidoethyl,
3-ureidopropyl, 4-hydroxycyclohexyl, 2,3,4-trihydroxybutyl, 2-sulfamoylaminoethyl, hydroxy group, aryl group, carboxy group, sulfo group, acylamino group, ureido group, sulfamoylamino A group, a sulfonylamino group, a carbamoyl group, and a sulfamoyl group. More preferably, methyl, ethyl, n-propyl, 2-hydroxyethyl,
3-hydroxypropyl, 4-hydroxybutyl, 2,
3-dihydroxypropyl, 3,4-dihydroxybutyl, 2-methanesulfonamidoethyl, 2-carboxyethyl, 4-sulfobutyl, 2-ureidoethyl, 2-
Carbamoylethyl, 2-sulfamoylethyl, 2-
Sulfamoylaminoethyl, hydroxy group, carboxy group, sulfo group, sulfonylamino group, carbamoyl group, sulfamoyl group.

N represents an integer of 0 to 2. n is preferably 0 to 1, and more preferably n is 0.

Z is a group of non-metal atoms containing at least one atom other than carbon and forming a 5- or 6-membered aromatic ring, and the aromatic ring may have a substituent. The atom other than carbon is a nitrogen atom, an oxygen atom or a sulfur atom, preferably a nitrogen atom or an oxygen atom. Examples of the aromatic ring are pyrrole, pyrazole, imidazole, pyridine, pyridazine, pyrimidine, pyrazine, furan, isoxazole, oxazole, thiophene, isothiazole and thiazole, preferably pyrrole, furan and thiophene (these are substituted. More preferred are pyrrole and furan (these may have a substituent). The substituents of these aromatic rings have the same meaning as the substituents described for R ³ .

As a combination of R ¹ , R ² , R ³ and Z, R ¹ and R ² are preferably unsubstituted or have a hydroxy group or a sulfonylamino group as a substituent.
8 is a linear, branched, or cyclic alkyl group, R ³ is a hydrogen atom, and Z is pyrrole, furan, or thiophene. More preferably, R ¹ and R ² are unsubstituted or have a hydroxy group or a sulfonylamino group as a substituent, and a linear or branched alkyl group having 1 to 4 carbon atoms, R ³
Is a hydrogen atom, and Z is pyrrole or furan. Specifically, preferably (R ¹ , R ² , R ³ , Z)
= (2-hydroxyethyl, 2-hydroxyethyl, hydrogen atom (n = 0), pyrrole), (ethyl, ethyl, hydrogen atom (n = 0), pyrrole), (ethyl, 2-hydroxyethyl, hydrogen atom ( n = 0), pyrrole), (3-
Hydroxypropyl, 3-hydroxypropyl, hydrogen atom (n = 0), pyrrole), (4-hydroxybutyl,
4-hydroxybutyl, hydrogen atom (n = 0), pyrrole), (2-methylsulfonylaminoethyl, 2-methylsulfonylaminoethyl, hydrogen atom (n = 0), pyrrole), (2-hydroxyethyl, 2- Hydroxyethyl, hydrogen atom (n = 0), furan), (3-hydroxypropyl, 3-hydroxypropyl, hydrogen atom (n =
0), furan), (4-hydroxybutyl, 4-hydroxybutyl, hydrogen atom (n = 0), furan), (ethyl, 2-carboxyethyl, hydrogen atom (n = 0), furan), (3, 4-dihydroxybutyl, 3,4-dihydroxybutyl, hydrogen atom (n = 0), furan), (ethyl, 3-hydroxypropyl, hydrogen atom (n = 0), furan), (2-hydroxyethyl, 3- Hydroxypropyl, hydrogen atom (n = 0), furan) (methyl, methyl, hydrogen atom (n = 0), pyrrole), (2,3,4-
Trihydroxybutyl, 2,3,4-trihydroxybutyl, hydrogen atom (n = 0), pyrrole), and more preferably (R ¹ , R ² , R ³ , Z) = (methyl, methyl, hydrogen atom (N = 0), pyrrole) (2-hydroxyethyl, 2-hydroxyethyl, hydrogen atom (n = 0),
(Pyrrole), (3-hydroxypropyl, 3-hydroxypropyl, hydrogen atom (n = 0), pyrrole), (4-
Hydroxypropyl, 4-hydroxypropyl, hydrogen atom (n = 0), pyrrole), (2-methylsulfonylaminoethyl, 2-methylsulfonylaminoethyl, hydrogen atom (n = 0), pyrrole), (2-hydroxyethyl) , 2-hydroxyethyl, hydrogen atom (n = 0), furan), (3-hydroxypropyl, 3-hydroxypropyl, hydrogen atom (n = 0), furan), (4-hydroxybutyl, 4-hydroxybutyl, Hydrogen atom (n =
0) and Fran).

Specific examples of typical developing agents represented by formula (D) in the invention are shown below, but the invention is not limited thereto.

[0021]

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[0022]

[Chemical 4]

[0023]

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[0024]

[Chemical 6]

[0025]

[Chemical 7]

[0026]

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[0027]

[Chemical 9]

[0028]

[Chemical 10]

Since the compound represented by the general formula (D) is very unstable when stored as a free amine,
In general, it is preferable to produce and store a salt of an inorganic acid or an organic acid so that a free amine is not formed until the salt is added to the treatment liquid. Examples of the inorganic or organic acid for forming the salt of the compound of the general formula (D) include hydrochloric acid, sulfuric acid, phosphoric acid, p-toluenesulfonic acid, methanesulfonic acid, naphthalene-
1,5-disulfonic acid and the like can be mentioned. Of these, salts of sulfuric acid and p-toluenesulfonic acid are preferable, and salts of sulfuric acid are most preferable.

(Synthesis Example) <Synthesis of Exemplified Compound (D-1)> The exemplified compound (D-1) of the present invention was synthesized according to the following formula.

[0031]

[Chemical 11]

(Synthesis of Compound (2)) 21.1 g of reduced iron, 0.2 g of ammonium chloride, 0.2 ml of acetic acid and 20 ml of water were placed in a 3-necked flask, and the mixture was stirred at an internal temperature of 88 ° C. for 30 minutes. I spilled. 100 ml of isopropyl alcohol was added thereto, and the mixture was further stirred for 10 minutes while heating under reflux, and then 4-nitroindole (Beilstein No. 2
Volume 0, No. 3, page 3194 describes the synthesis method.) 1
0.2 g was added over 5 minutes, and the mixture was further stirred for 2 hours while heating under reflux. The reaction solution was filtered through Celite, and the residue obtained by concentrating the filtrate with a rotary evaporator was directly used in the next step. (Synthesis of Compound (3)) Compound (2) obtained in the previous step
Tetrahydrofuran (30 ml) was added to and dissolved, and 20.6 g of bromoethane was added dropwise with stirring under heating under reflux, 10.6 g of sodium hydrogen carbonate was added, and the mixture was stirred under heating under reflux for 2 hours. After cooling to room temperature, 100 ml of ethyl acetate and 50 ml of water were added for extraction. The obtained ethyl acetate layer was washed 3 times with a mixed solution of 30 ml of saturated saline solution and 50 ml of water, dried over anhydrous sodium sulfate, and concentrated by a rotary evaporator. The obtained residue was purified by silica gel column chromatography to obtain 5.5 g of the desired compound (3) (yield from compound (1) 46%). NMR (DMSO-d6): δ = 10.93 (brs,
1H), 7.1 to 7.2 (m, 1H), 6.8 to 7.0.
(M, 2H), 6.3 to 6.5 (m, 2H), 3.31
(Q, 4H, J = 6.9 Hz), 0.96 (t, 6H,
J = 6.9 Hz) (Synthesis of compound (4)) 2,5-dichloroaniline 6.
While adding 17.1 ml of hydrochloric acid to 48 g and stirring under ice cooling, an aqueous solution in which 3.04 g of sodium nitrite was dissolved in 6 ml of water was added dropwise over 5 minutes, and stirring was continued for 10 minutes thereafter. . On the other hand, to 5.00 g of the compound (3), 13.1 g of sodium acetate and 50 ml of methanol were added, and the reaction solution prepared from 2,5-dichloroaniline was added thereto over 5 minutes while stirring under ice cooling. added. Then, after stirring for 30 minutes, 200 ml of ethyl acetate and 100 ml of water were added.
Was added and extraction was performed. The obtained ethyl acetate layer was washed 3 times with a mixed solution of 30 ml of saturated saline and 70 ml of water, dried over anhydrous sodium sulfate, and then concentrated by a rotary evaporator. 5 ml of the obtained residue is tetrahydrofuran.
Dissolved in a mixed solution of 20 ml of ethyl acetate and ethyl acetate, and then cooled with ice,
The precipitated crystals are suction filtered to obtain the desired compound (4).
9 g was obtained (yield 51%). NMR (DMSO-d6): δ = 11.62 (brs,
1H), 7.82 (d, 1H, J = 2.0Hz), 7,
72 (d, 1H, J = 8.7 Hz), 7.65 (d, 1
H, J = 8.7 Hz), 7.4 to 7.5 (m, 1H),
7.33 (dd, 1H, J = 2.0, 8.7 Hz),
6.7 to 6.8 (m, 1H), 6.60 (d, 1H, J
= 8.7 Hz), 3.76 (q, 4H, J = 6.7H)
z), 1.33 (t, 6H, J = 6.7 Hz) (Synthesis of Exemplified Compound (D-1)) Compound (4) was 4.9
0.5 g of 10% palladium / carbon catalyst and 30 ml of ethanol were added to g, and the mixture was stirred at room temperature for 8 hours with hydrogen in the autoclave at 50 atm. The obtained reaction mixture was filtered through Celite, and the filtrate was concentrated with a rotary evaporator. The residue was purified by silica gel column chromatography, and naphthalene-1,5-disulfonic acid 2.
A solution prepared by dissolving 4 g in 10 ml of ethanol was added, and the precipitated crystals were suction-filtered to obtain 0.90 g of naphthalene-1,5-disulfonic acid salt of the target exemplary compound (D-1) (yield 14%). NMR (DMSO-d6): δ = 10.71 (brs,
1H), 8.91 (d, 2H, J = 8.7Hz), 8.
00 (d, 2H, J = 8.7 Hz), 7.5 to 7.7
(M, 1H), 7.47 (dd, 2H, J = 8.7,
8.7 Hz), 7.25 (d, 1H, J = 8.7 Hz)
6.8-7.0 (m, 2H), 6.80 (brs, 4
H), 3.70 (q, 4H, J = 6.7 Hz), 0.9
0 (t, 6H, J = 6.7Hz)

<Synthesis of Exemplified Compound (D-10)> Exemplified compound (D-10) of the present invention was synthesized according to the following formula.

[0034]

[Chemical 12]

(Synthesis of Compound (7)) To 139.1 g of Compound (5), 207 g of potassium carbonate, 10 g of sodium iodide, and 450 ml of N, N-dimethylformamide were added, and the mixture was heated with stirring at an internal temperature of 85 ° C. While going here 128
Compound (6) (g) was added dropwise over 10 minutes. As it is 3
After heating and stirring for an hour, the mixture was allowed to cool to room temperature, and 1000 ml of ethyl acetate and 1200 ml of water were added for extraction. The obtained ethyl acetate layer was diluted with 300 ml of saturated saline and 500 m of water.
After being washed 5 times with 1 l of the mixed solution, it was dried over anhydrous sodium sulfate and concentrated by a rotary evaporator. The target compound (7) was obtained from the obtained residue by distillation to give 194.
6 g was obtained (yield 93%). NMR (CDCl ₃ ): δ = 7.85 (dd, 1H, J =
3.0, 9.0 Hz) 7.66 (d, 1H, J = 3.0
Hz), 7.46 (dd, 1H, J = 9.0, 9.0H
z), 7.20 (dd, 1H, J = 3.0, 9.0H
z), 4.75 (q, 1H, J = 7.0 Hz), 2.2
3 (s, 3H), 1.56 (d, 3H, J = 7.0H
z) (Synthesis of compound (8)) 130.5 g of the compound (7) was dissolved in 400 ml of methylene chloride, and 175 ml of sulfuric acid was added dropwise thereto over 30 minutes while stirring with heating under reflux. Stirring was continued for 4 hours while heating under reflux, and the mixture was allowed to cool to room temperature and poured into 1 kg of ice. Ethyl acetate 1
000 ml and 200 g of sodium chloride were added for extraction, and the obtained ethyl acetate layer was washed 3 times with a mixed solution of 300 ml of saturated saline and 300 ml of water. After drying over anhydrous sodium sulfate, 200 ml of methanol was added to the residue concentrated by a rotary evaporator, and the precipitated crystals were suction filtered to obtain 53 g of the objective compound (8) (yield 44%). NMR (CDCl ₃ ): δ = 7.90 (d, 1H, J =
9.0 Hz), 7.60 (d, 1H, J = 9.0H
z), 7.23 (dd, 1H, J = 9.0, 9.0H
z), 2.45 (s, 3H), 2.27 (s, 3H) (Synthesis of compound (9)) 20 mg of water was added to 36.5 g of reduced iron, 1 g of ammonium chloride and 1 ml of acetic acid, and the internal temperature was 85.
After heating and stirring at 10 ° C. for 10 minutes, 100 ml of isopropyl alcohol was added thereto, and the mixture was heated and refluxed for 10 minutes. To this, 24.0 g of the compound (8) was added, and the mixture was further heated and refluxed with stirring for 3 hours and then filtered through Celite.
The obtained filtrate was concentrated to obtain compound (9) as a crude product. This product was directly used in the next step. (Synthesis of Compound (10)) Compound (9) obtained in the previous step
To the mixture were added 68.0 g of potassium carbonate and 100 ml of N, N-dimethylformamide, and the mixture was heated with stirring at an internal temperature of 60 ° C. After 52.6 g of ethyl bromoacetate was added dropwise thereto over 10 minutes, heating stirring was continued at 60 ° C. for 2 hours. After cooling to room temperature, 500m of ethyl acetate
1 and 500 ml of water were added for extraction. The obtained ethyl acetate layer was washed 4 times with a mixed solution of saturated saline (100 ml) and water (300 ml), dried over anhydrous sodium sulfate and concentrated by a rotary evaporator to obtain the target compound (10) as a crude product. . This product was directly used in the next step. (Synthesis of Compound (11)) 8.0 g of lithium aluminum hydride was suspended in 50 ml of tetrahydrofuran, and a solution of the compound (10) obtained in the previous step in 50 ml of tetrahydrofuran was added dropwise thereto over 10 minutes. The mixture was stirred as it was at room temperature for 5 hours and then stirred for 1 hour under heating and refluxing conditions. 30 ml of ethyl acetate is added here to 10
After dropwise addition over a period of 1 minute, stirring was continued for 1 hour, 5 ml of a saturated aqueous sodium sulfate solution was added dropwise, and the mixture was stirred for 10 minutes. This was filtered through Celite, and the filtrate was concentrated by a rotary evaporator to obtain the target compound (11) as a crude product. This product was directly used in the next step. (Synthesis of Compound (12)) To 23.6 g of 2,5-dichloroaniline, 62 ml of hydrochloric acid and 400 ml of methanol were added and dissolved, and 11.1 g of sodium nitrite was dissolved in 22 ml of water while stirring under ice cooling. The solution was added dropwise over 10 minutes. On the other hand, 45 g of sodium acetate and 100 ml of methanol were added to the compound (11) in the previous step, the mixture was stirred under ice cooling, and the reaction solution prepared from 2,5-dichloroaniline was added thereto. After stirring for 30 minutes, 1000 ml of ethyl acetate and 800 ml of water were added for extraction, and the obtained ethyl acetate layer was diluted with 200 ml of saturated saline and 400 m of water.
It was washed 4 times with 1 l of the mixed solution. After drying over anhydrous sodium sulfate, the mixture was concentrated with a rotary evaporator, and the obtained residue was purified by silica gel column chromatography to obtain 19.6 g of the target compound (12) (yield 37 from compound (8). %). NMR (DMSO-d6): δ = 7.6 to 7.7 (m,
3H), 7.45 (dd, 1H, J = 10.0, 3.0
Hz), 6.56 (d, 1H, J = 10.0 Hz) 3.
6 to 3.7 (m, 4H), 3.3 to 3.5 (m, 4)
H), 2.51 (s, 3H), 2.40 (s, 3H) (Synthesis of Exemplified Compound (D-10)) 20 ml of ethanol was added to 4.90 g of compound (12) and stirred. 0.5 g of 10% palladium / carbon catalyst was added thereto, and 5 ml of formic acid was added dropwise thereto over 5 minutes. After stirring for 30 minutes as it is, naphthalene 1,
An ethanol solution of 2.1 g of 5-disulfonic acid was added. The obtained crystals are suction-filtered to obtain the desired exemplary compound (D
-10) naphthalene 1,5-disulfonate to 3.0
0 g was obtained (yield 47%). NMR (DMSO-d6): δ = 8.86 (d, 2H,
J = 9.0 Hz), 7.95 (d, 2H, J = 9.0H)
z), 7.41 (dd, 2H, J = 9.0, 9.0H
z), 6.97 (d, 1H, J = 9.0 Hz), 6.6
3 (d, 1H, J = 9.0 Hz), 3.67 (t, 4
H, J = 5.0 Hz), 3.27 (t, 4H, J = 5.
0 Hz), 2.36 (s, 3H), 2.33 (s, 3)
H)

<Synthesis of Exemplified Compound (D-41)> Exemplified compound (D-41) of the present invention was synthesized according to the following formula.

[0037]

[Chemical 13]

(Synthesis of Compound (13)) 43.3 g (0.30 M) of δ-aminoquinoline, 41.5 g of potassium carbonate
To a 200 ml mixture of N and N-dimethylacetamide, 46.8 g (0.30
M) was added dropwise, and the mixture was reacted at 65 ° C. for 2 hours. After cooling, 500 ml of water was added to the reaction solution, extracted with 500 ml of ethyl acetate, and washed with water (200 ml × 3 times). The extract was concentrated, and separated and purified by silica gel column chromatography (developing solvent: ethyl acetate: hexane mixed solution) to obtain 34.7 g (67%) of the desired compound (13). (Synthesis of Compound (14)) (13) 34.7 (0.20 M),
To a mixed solution of 41.5 g (0.30 M) of potassium carbonate, 18 g (0.12 M) of sodium iodide and 100 ml of N, N-dimethylacetamide, with stirring at 120 ° C., 3
-Chloropropyl alcohol 39.8 g (0.42M)
Was added dropwise, and the reaction was continued for 10 hours. Furthermore, K ₂ CO ₃ 4
1.5 g and 3-chloropropyl alcohol 19.9
g, and after reacting at 120 ° C. for 1 hour, 31a
In the same manner as in (1) above, the mixture was post-treated and purified by silica gel column chromatography to obtain 29.8 g (65%) of the desired product (14). (Synthesis of Compound (15)) 8.9 g (0.055 M) of 2,5-dichloroaniline was dissolved in a mixed solution of 20 ml of 12N hydrochloric acid and 10 ml of tetrahydrofuran, and 3.8 g (0 0.055M) aqueous solution (15 ml) and added dropwise over 10 minutes. Further at 1.degree.
After reacting for 5 hours, 11.5 g (0.
050M) and sodium acetate 24.6g (0.30M)
Was added dropwise to a methanol (80 ml) solution of with stirring under ice cooling. After reacting at 0 ° C. for 1 hour and at room temperature for 2 hours, 150 ml of water was added to the reaction solution, and 200 ml of ethyl acetate was added.
extracted with ml. After washing and concentrating with water, the product (15) was purified with silica gel column chromatography to give 16.
1 g (72.5%) was obtained. (Synthesis of Exemplified Compound (D-41)) Compound (15) 8.1
g (0.020M), 10% palladium / carbon 1.0g
Was dispersed in 150 ml of ethanol and reacted at 40 ° C. under a hydrogen atmosphere of 30 atm. The reaction mixture was filtered through Celite, 1,5-naphthalenedisulfonic acid tetrahydrate (3.6 g) was added to the filtrate, and the precipitated crystals were collected by filtration to obtain the desired product (D-
41) 1,5-naphthalenedisulfonate 7.5 g
(70%). NMR spectrum (D ₂ O): δ 0.92 (t, 3
H), 1.75 (m, 2H), 3.5 (t, 2H),
3.7 (m, 4H), 7.4 (d, 1H), 7.7 (t
+ M, 2H + 1H), 7.9 (d, 1H), 8.15
(D, 2H), 8.45 (m, 1H), 8.8 (d, 2
H), 8.95 (m, 1H)

The color developing agent of the present invention can be used alone or in combination with other known p-phenylenediamine derivatives. Representative examples of the compound to be combined are shown below, but the invention is not limited thereto. N, N-diethyl-p-phenylenediamine (P-1), 4-amino-
3-methyl-N, N-diethylaniline (P-2), 4
-Amino-3-methyl-N-ethyl-N- (3-hydroxypropyl) aniline (P-3), 4-amino-N-
Ethyl-N- (2-hydroxyethyl) aniline (P-
4), 4-amino-3-methyl-N-ethyl-N- (2
-Hydroxyethyl) aniline (P-5), 4-amino-3-methyl-N-ethyl-N- (2-methanesulfonamidoethyl) aniline (P-6), N- (2-amino-5-N , N-diethylaminophenylethyl) methanesulfonamide (P-7), N, N-dimethyl-p-phenylenediamine (P-8), 4-amino-3-methyl-N-ethyl-N- (2-methoxy). Ethyl) aniline (P-9), 4-amino-3-methyl-N-ethyl-N
-(4-hydroxybutyl) aniline (P-10), 4-
Amino-3-methyl-N-ethyl-N- (2-butoxyethyl) aniline (P-11). Of the above-mentioned p-phenylenediamine derivatives, the compound to be combined is particularly preferably P-3, P-5, P-6 or P-10.
In addition, these p-phenylenediamine derivatives are generally used in salts such as sulfates, hydrochlorides, sulfites, p-toluenesulfonates, nitrates, naphthalene-1,5-disulfonates. . The treatment composition may be liquid or solid (eg, powder, granules, tablets)
It may be. Two or more of these compounds can be used in combination depending on the purpose. The amount of the aromatic primary amine developing agent used is preferably 0.0 per 1 liter of the color developing solution.
The amount is 01 mol to 0.2 mol, and more preferably 0.005 mol to 0.1 mol.

The color developing solution is described in JP-A-63-5341, JP-A-63-106655 or JP-A-4-144446 as a compound which directly preserves the aromatic primary amine color developing agent. Various hydroxylamines, hydroxamic acids described in JP-A-63-43138, hydrazines and hydrazides described in JP-A-63-146041, 63-44657 and 63-58.
It can contain phenols described in No. 443, α-hydroxyketones and α-aminoketones described in No. 63-44656, various sugars described in No. 63-36244, and the like. In addition, in combination with the above compounds, JP-A Nos. 63-4235, 63-24254 and 63-2
1647, 63-146040, 63-278.
41 and 63-25654 and the like, monoamines, 63-30845, 63-14640,
Diamines described in 63-43139 and the like, 63-
21647, 63-26655 and 63-4
Polyamines described in No. 4655, 63-53551.
No. 63-43140
Nos. 63-53549 and 63-56654, and oximes and 63-
The tertiary amines described in No. 239447 can be used. Other preservatives include JP-A-57-44148.
And various metals described in No. 57-53749, salicylic acids described in No. 59-180588, No. 54-
Alkanolamines described in 3582, 56-9
The polyethyleneimine described in 4349, the aromatic polyhydroxy compound described in U.S. Pat. No. 3,746,544 and the like may be contained as necessary. Especially when hydroxylamines are used, it is preferable to use the above-mentioned alkanolamines and aromatic polyhydroxy compounds in combination.
Particularly preferred preservatives are disclosed in JP-A-3-144446.
Among them, hydroxylamines represented by the general formula (I) of the above-mentioned No. 1, and among them, compounds having a methyl group, an ethyl group, a sulfo group or a carboxy group are preferable. The amount of these preservatives added is 20 mmol to 200 mmol, preferably 30 mmol to 150, per liter of color developing solution.
It is millimoles.

It is preferable that the developing solution for the light-sensitive material for printing contains chlorine ions in an amount of 3.0 × 10 ^{-2 to} 1.5 × 10 ^-1 mol / liter. Particularly preferably 3.5 × 10
^{It is −2 to} 1.0 × 10 ⁻¹ mol / liter. When the chlorine ion concentration is more than 1.5 × 10 ^{−1 to} 1.0 × 10 ⁻¹ mol / liter, it has a drawback that development is delayed, and in order to achieve the object of the present invention that the concentration is rapid and the maximum concentration is high. Not preferable. Further, if it is less than 3.0 × 10 ^-2 mol / liter, it is not preferable for preventing fog. In the present invention, it is preferable that the color developer contains 0.5 × 10 ⁻⁵ mol / liter to 1.0 × 10 ⁻³ mol / liter of bromine ions. More preferably, it is 3.0 × 10 ^{−5 to} 5 × 10 ⁻⁴ mol / liter. When the bromine ion concentration is higher than 1 × 10 ^-3 mol / liter, development is delayed, the maximum concentration and sensitivity are lowered, and when it is less than 0.5 × 10 ^-5 mol / liter, fog is sufficiently prevented. I can't.

Here, the chlorine ion and the bromine ion may be directly added to the color developing solution or may be eluted from the light-sensitive material into the color developing solution during the development processing. When added directly to the color developer, examples of the chloride ion supplying substance include sodium chloride, potassium chloride, ammonium chloride, lithium chloride, magnesium chloride and calcium chloride. Further, it may be supplied from a fluorescent whitening agent added to the color developing solution. As a source of bromide ions,
Examples thereof include sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide and magnesium bromide. When it is eluted from the light-sensitive material during the development processing, both chlorine ions and bromine ions may be supplied from the emulsion or may be supplied from sources other than the emulsion.

For other color developers, the above-mentioned JP-A-3-
Various additives described in No. 144446 can be used. For example, carbonic acid, phosphoric acid, boric acid, hydroxybenzoic acid, etc. of the same patent page (9) can be used as a buffering agent for maintaining pH. It is preferable that the pH of the color developer is maintained at 9.0 to 12.5 by using these buffers. More preferably, it is 9.5 to 11.5. Examples of the antifoggants include halide ions and organic antifoggants described on page (10). In particular, when the concentration of the developing agent in the color developing solution is as high as 20 mmol / liter or higher, or when high-temperature processing is performed at 40 ° C. or higher, the bromide ion concentration is preferably higher to some extent.
It is preferably from liter to 60 mmol. If necessary, the halogen can be removed by using an ion exchange resin or an ion exchange membrane to control the concentration within a preferable range. As the chelating agent, aminopolycarboxylic acid,
Aminopolyphosphonic acid, alkylphosphonic acid and phosphonocarboxylic acid are preferably used. For example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1.
-Diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof are representative examples. The compound can be used. Further, as a preferable chelating agent, a compound having biodegradability can be mentioned. Examples of this are JP-A-63-146998 and JP-A-63-19929.
5, JP-A-63-267750, JP-A-63-26
7751, JP-A-2-229146, JP-A3-1
86841, German Patent 3739610, European Patent 46
8325 and the like. Furthermore, development inhibitors such as benzimidazoles, benzothiazoles or mercapto compounds, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, competitive couplers, 1-phenyl- An auxiliary developing agent such as 3-pyrazolidone, a viscosity imparting agent, or various surfactants such as alkylsulfonic acid, arylsulfonic acid, aliphatic carboxylic acid and aromatic carboxylic acid may be added as necessary.

If desired, an optional development accelerator can be added to the color developing solution. As a development accelerator, Japanese Patent Publication No. 37
-16088, 37-5987, 38-782.
No. 6, No. 44-12380, No. 45-9019, and thioether compounds represented by US Pat. No. 3,813,247;
P-phenylenediamine compounds represented by JP-A-15554, JP-A-50-137726, and JP-B-44-3.
No. 0074, JP-A Nos. 56-156826 and 52-
Quaternary ammonium salts represented by U.S. Pat. No. 4,434,29, US Pat. Nos. 2,494,903 and 3,128,182.
No. 4,230,796, 3,253,919
No. 4, Japanese Patent Publication No. 41-11431, US Pat. No. 2,48
2,546, 2,596,926 and 3,58
Amine compounds described in 2,346, etc., JP-B-37-
16088, 42-25201, U.S. Pat.
128,183, Japanese Patent Publication Nos. 41-11431, 42
-23883 and U.S. Pat. No. 3,532,501 and the like, polyalkylene oxides, other 1-phenyl-3-pyrazolidones, imidazoles, and the like can be added as necessary.

In the case of a light-sensitive material for photographing, the replenishing amount of the color developing solution is preferably 550 ml or less per 1 m ² , and 450 ml.
The following is more preferable, and 400 ml or less and 80 ml or more are most preferable. The bromide ion concentration in the replenisher can be reduced to 300 ml or less by reducing or not containing it. In the case of a photosensitive material for printing, the replenishing amount of the color developing solution is suitably 20 to 600 ml, preferably 30 to 200 ml, and more preferably 40 to 100 ml per 1 m ^{2 of} the photosensitive material. In the case of a photographic light-sensitive material, the processing temperature of the color developing solution is preferably 35 ° C or higher, more preferably 40 ° C or higher and 50 ° C or lower. In the case of a photosensitive material for printing, the processing temperature of the color developing solution is 20 to 50 ° C, preferably 30 to
45 ° C, most preferably 37-42 ° C. The processing time of the color developing solution is preferably 30 seconds to 3 minutes and 15 seconds, and more preferably 30 seconds to 2 minutes and 30 seconds in the case of a photographic light-sensitive material. In the case of a photosensitive material for printing, the processing time of the color developing solution is generally 3 minutes or less, preferably 10 seconds to 1 minute, more preferably 10 seconds to 30 seconds. Here, the processing time (for example, development time) refers to the time from when the photosensitive material enters the target processing solution to when it enters the next processing solution.

It is preferable that the developing solution for the light-sensitive material for printing contains substantially no benzyl alcohol. The developer of the photosensitive material for printing suppresses fluctuations in photographic characteristics due to continuous processing, and contains substantially no sulfite ion in order to achieve the effects of the present invention. , And the sulfite ion concentration is 3.0 × 10 ⁻³ mol / liter or less). Sulfite ion is preferably 1.0 × 10 ⁻³ mol / liter or less, and most preferably contains no sulfite ion. Here, however, a very small amount of sulfite ion used for the oxidation prevention of the processing agent kit in which the developing agent is concentrated before preparing the use solution is excluded. In order to suppress fluctuations in photographic characteristics due to fluctuations in the concentration of hydroxylamine, the developer should also be substantially free of hydroxylamine (substantially free of hydroxylamine here means a hydroxylamine concentration of 5.0 × 1).
It is 0 ^-3 mol / liter or less. ) Is more preferable. Most preferably, it contains no hydroxylamine at all.

Further, it is preferable to prevent liquid evaporation and air oxidation. The contact area between the photographic processing liquid and air in the processing tank can be represented by the aperture ratio defined below. That is, aperture ratio = [contact area between treatment liquid and air (cm ² )] ÷
[Treatment Liquid Volume (cm ³ )] The aperture ratio (cm ⁻¹ ) is preferably 0.05 or less, and more preferably 0.0005 to 0.01.
As a method for reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the photographic processing liquid surface of the processing tank, a method using a movable lid described in JP-A-1-82033,
The slit development processing method described in JP-A-63-216050 can be mentioned. Further, it is preferable that the replenishing tank of the color developing solution or the processing solution in the processing layer is shielded with a high boiling point organic solvent or a high molecular compound to reduce the contact area with air. Liquid paraffin and organosiloxane are particularly preferable. Reducing the aperture ratio can be applied not only in both the color development step and the black and white development step, but also in the subsequent steps such as bleaching, bleach-fixing, fixing, washing and stabilizing. The developer can be regenerated and used. Regeneration of the developing solution means that the used developing solution is subjected to anion exchange resin or electrodialysis, or the processing solution called a regenerant is added to increase the activity of the developing solution and to use it again as a processing solution. . In this case, the regeneration rate (ratio of overflow solution in replenisher) is
70% or more is preferable, and 90% or more is particularly preferable. As a regeneration method, it is preferable to use an anion exchange resin. Particularly preferred anion exchange resin compositions and resin regeneration methods include those described in DIAION Manual (I) (14th edition, 1986) issued by Mitsubishi Kasei Co., Ltd. Further, among the anion exchange resins, JP-A-2-952 and JP-A-1-28115 are available.
Resins having the composition described in No. 2 are preferable.

The color-developed light-sensitive material is usually desilvered. The desilvering process here basically comprises a bleaching process and a fixing process, but it is constituted by combining a bleach-fixing process in which these processes are performed simultaneously and these processes. Examples of bleaching agents include iron salts; iron (III), cobalt (III)
, Compounds of polyvalent metals such as chromium (IV) and copper (II); peracids; quinones; nitro compounds and the like. Typical bleaching agents are iron chloride; ferricyanide; dichromate; organic complex salts of iron (III) (eg ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diamino). Metal complex salts such as aminopolycarboxylic acids such as propane tetraacetic acid, glycol ether diamine tetraacetic acid); persulfates; bromates; permanganates; nitrobenzenes and the like. Among these, the above-mentioned JP-A-3-
A ferric aminopolycarboxylic acid salt or a salt thereof is preferably used as described on page 144446 (11). For example, ferric salts such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid and glycol etherdiaminetetraacetic acid can be used. In addition, as the bleaching agent, complex salts of citric acid, tartaric acid, malic acid and the like can be used. Among these, aminopolycarboxylic acid iron (III) complex salts including ethylenediaminetetraacetic acid iron (III) complex salts and 1,3-diaminopropanetetraacetic acid iron (III) complex salts are particularly preferable. These aminopolycarboxylic acid iron (III) complex salts are particularly useful in both the bleaching solution and the bleach-fixing solution.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath.
Specific examples of useful bleaching accelerators are described in the following specifications: US Pat. No. 3,893,858, West German Patent 1,290,812, JP-A-53-95630, Research. Disclosure No. 17129 (197
Compounds having a mercapto group or a disulfide bond described in JP-A No. 50-140129; U.S. Pat. No. 3,706,5.
No. 61, a thiourea derivative; JP-A-58-1623.
Iodide salt described in No. 5; West German Patent No. 2,748,430
Compounds described in Japanese Patent Publication No. Sho 45-
The polyamine compound described in No. 8836; bromide ion and the like can be used. Among them, a compound having a mercapto group or a disulfide group is preferable from the viewpoint of a large accelerating effect,
Especially US Pat. No. 3,893,858, West German Patent No. 1,
Compounds described in JP-A No. 290,812 and JP-A No. 53-95630 are preferable. Further, US Pat. No. 4,552,8
The compounds described in No. 34 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography.

In the desilvering bath, in addition to the bleaching agent, Japanese Patent Laid-Open No. 3-1
No. 44446 (12), rehalogenating agent, p.
H buffer and known additives can be used. The bleaching solution and the bleach-fixing solution preferably contain an organic acid in order to prevent bleaching stain in addition to the above compounds. Particularly preferred organic acids are compounds having an acid dissociation constant (pka) of 2 to 6, specifically, acetic acid, propionic acid, hydroxyacetic acid succinic acid, maleic acid, glutaric acid, fumaric acid, malonic acid, adipic acid, etc. However, succinic acid, maleic acid and glutaric acid are particularly preferable. The pH of the bleaching solution or the bleach-fixing solution is usually 4.0 to 8.0, but a lower pH can be used for speeding up the processing.

Examples of the fixing agent used in the fixing solution and the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas and a large amount of iodide salts. It is commonly used, especially ammonium thiosulfate being the most widely used. Further, the combined use of thiosulfate with thiocyanate, thioether compound, thiourea and the like is also preferable. As a preservative for the fixing solution and the bleach-fixing solution, sulfites, bisulfites, carbonyl bisulfite adducts or sulfinic acid compounds described in EP 294769A are preferable. Further, for the purpose of stabilizing the liquid, it is preferable to add various aminopolycarboxylic acids and chelating agents such as organic phosphonic acids. Preferred chelating agents include 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediamine-N, N, N ', N'-tetrakis (methylenephosphonic acid), nitrilotrimethylenephosphonic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexane. Diamine tetraacetic acid, 1,2
Mention may be made of propylenediaminetetraacetic acid. Among these, 1-hydroxyethylidene-1,1-diphosphonic acid and ethylenediaminetetraacetic acid are particularly preferable. The fixing solution and the bleach-fixing solution have a pKa of 6.
It is preferable to contain a compound of 0 to 9.0. For example, it is preferable to add imidazoles such as imidazole, 1-methylimidazole, 1-ethylimidazole, and 2-methylimidazole in an amount of 0.1 to 10 mol / liter. The imidazole compound represents imidazole and derivatives thereof, and preferable substituents of imidazole include an alkyl group, an alkenyl group, an alkynyl group, an amino group, a nitro group, a halogen atom and the like.
The alkyl group, alkenyl group and alkynyl group may be further substituted with an amino group, a nitro group, a halogen atom or the like. The preferred total carbon number of the substituents of the imidazole is 1 to 6, and the most preferred substituent is the methyl group.

Specific examples of the imidazole compound are shown below, but the invention is not limited thereto. Imidazole, 1-methylimidazole, 2-methylimidazole, 4-methylimidazole, 4- (2-hydroxyethyl) -imidazole, 2-ethylimidazole, 2-
Vinyl imidazole, 4-propyl imidazole, 4-
(2-Aminoethyl) imidazole, 2,4-dimethylimidazole, 2-chloroimidazole. Of these,
Preferred compounds are imidazole, 2-methyl-imidazole, 4-methyl-imidazole, most preferred compounds are imidazole.

The fixing solution and the bleach-fixing solution may further contain various fluorescent whitening agents, defoaming agents, surfactants, polyvinylpyrrolidone, methanol and the like. When the replenishing system is adopted in the processing, the replenishing amount of the fixing solution or the bleach-fixing solution is 100 to 3000 per 1 m ² of the light-sensitive material.
ml is preferred, but more preferably 300-1800 m
It is l. The replenishment of the bleach-fixing solution may be conducted as a bleach-fixing replenishing solution, or as described in JP-A-61-143755 and Japanese Patent Application No. 2-216389, an overflow solution of a bleaching solution and a fixing solution is used. May be. The total processing time of the desilvering step, which is a combination of bleaching, bleach-fixing and fixing of the photographic light-sensitive material, is preferably 30 seconds to 3 minutes, more preferably 45 seconds to 2 minutes. The processing temperature is 30 to 60.
C., preferably 35 to 55.degree.

A processing solution having a bleaching ability is particularly preferably subjected to aeration during processing because the photographic performance is kept extremely stable. Means known in the art can be used for the aeration, and blowing of air into the processing liquid having a bleaching ability or absorption of air using an ejector can be performed. At the time of blowing air, it is preferable to discharge the air into the liquid through an air diffusing tube having fine pores. Such an air diffuser is widely used as an aeration tank in activated sludge treatment. Regarding aeration, Z-1 issued by Eastman Kodak Company
21, Youth Process C-41 3rd Edition (198)
2 years), and the matters described on pages BL-1 to BL-2 can be used. In the processing using the processing solution having a bleaching ability of the present invention, it is preferable that the stirring is intensified. To carry out this, page 8, upper right column, line 6 of JP-A-3-33847. ~ The contents described in the lower left column, second line can be used as they are.

A processing solution having a fixing ability can be subjected to silver recovery by a known method, and a regenerating solution subjected to such silver recovery can be used. The silver recovery method includes an electrolysis method (described in French Patent No. 2,299,667), a precipitation method (Japanese Patent Laid-Open No. 52-73037, and German Patent No. 2,331.
No. 220), ion exchange method (JP-A-51-1711).
4, described in German Patent No. 2,548,237) and the metal substitution method (described in British Patent No. 1,353,805) are effective. These silver recovery methods are preferable when they are carried out in-line from the tank solution because the suitability for rapid processing is further improved. Further, the processing solution having a bleaching ability can be reused after recovering the overflow solution after use in the processing, adding the components to correct the composition. Such usage is usually called regeneration, but the present invention can also favor such regeneration. Regarding the details of the reproduction, the matters described on pages 39 to 40 of Fuji Film Processing Manual, Fuji Color Negative Film, CN-16 processing (revised August 1990), published by Fuji Photo Film Co., Ltd. can be applied. The kit for adjusting the processing liquid having the bleaching ability of the present invention may be a liquid or a powder, but when the ammonium salt is excluded, most of the raw materials are supplied as a powder, and since the hygroscopicity is also small, Makes powder easier. From the viewpoint of reducing the amount of waste liquid, the regenerating kit is preferably a powder because it can be added directly without using excess water.

Regarding the regeneration of the processing solution having the bleaching ability,
In addition to the aeration mentioned above, "Basics of photographic engineering-silver salt photography-" (edited by the Photographic Society of Japan, published by Corona Publishing Co., 1979)
Year)) etc. can be used. Specifically, in addition to electric field regeneration, there is a method for regenerating bleaching solution with bromic acid, zincic acid, bromine, bromine precursor, persulfate, hydrogen peroxide, hydrogen peroxide using catalyst, bromic acid, ozone, etc. Can be mentioned.
In electrolytic regeneration, the cathode and the anode are put in the same bleaching bath, or the anode bath and the cathode bath are regenerated by using a diaphragm to separate the baths. The fixing solution can be reprocessed at the same time. The fixing solution and the bleach-fixing solution are regenerated by electrolytically reducing accumulated silver ions. Other,
It is also preferable to remove accumulated halogen ions with an anion exchange resin in order to maintain the fixing performance.

In the desilvering process, it is preferable that the stirring is strengthened as much as possible. As a concrete method for strengthening the stirring, there is a method described in JP-A-62-183460, in which a jet of a processing solution is made to collide with the emulsion surface of a light-sensitive material, and JP-A-6-62.
No. 183,461 rotating means to improve the stirring effect, and further, by moving the light-sensitive material while bringing the wiper blade provided in the liquid into contact with the emulsion surface to make the emulsion surface turbulent There are a method of improving the effect and a method of increasing the circulation flow rate of the whole processing solution. Such a stirring improving means is effective in any of a bleaching solution, a bleach-fixing solution and a fixing solution. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, and consequently the desilvering rate. Further, the above-mentioned stirring improving means is more effective when a bleaching accelerator is used, and it is possible to remarkably increase the accelerating effect and eliminate the fixing inhibiting effect of the bleaching accelerator. The automatic developing machine used for the light-sensitive material of the present invention is disclosed in JP-A-60-191257 and 60-19.
It is preferable to have the photosensitive material conveying means described in Nos. 1258 and 60-191259. As described in the above-mentioned JP-A-60-191257, such a conveying means can remarkably reduce the carry-in of the treatment liquid from the front bath to the rear bath, and is highly effective in preventing the performance deterioration of the treatment liquid. Such an effect is particularly effective for reducing the processing time in each step and reducing the replenishing amount of the processing solution.

After the desilvering process, a washing process is generally performed. A stable process may be performed instead of the water washing process. In such stabilization treatment, Japanese Patent Laid-Open No. 57-8543
All known methods described in Nos. 58-14834 and 60-220345 can be used. Also,
A water washing step-stabilization step may be performed in which a stabilizing bath containing a dye stabilizer and a surfactant is used as a final bath. The water washing solution and the stabilizing solution may contain a hard water softening agent such as inorganic phosphoric acid, polyaminocarboxylic acid, or organic aminophosphonic acid.

The amount of water in the rinsing step depends on the characteristics of the light-sensitive material (for example, depending on the material used such as a coupler), the application, the liquid temperature, the number of tanks (the number of stages), the replenishment method such as countercurrent and forward current, and various other types. It can be set in a wide range depending on the conditions. The number of stages is preferably 2 to 4. The replenishment amount is 1 to 50 times, preferably 1 to 30 times the amount brought in from the previous bath per unit area.
Times, more preferably 1 to 10 times. Further, as a method of efficiently reducing the replenishment amount, a so-called multi-chamber washing process in which the washing tank or stabilizing bath is divided by partition walls and the photosensitive material is processed in the liquid without passing through the slit portion of the wiper blade or the like into the air Alternatively, stabilizing treatment is preferably used.

According to the above-mentioned multi-stage countercurrent method or multi-chamber washing method, the amount of washing water can be greatly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate and the suspended matter produced is exposed to light. Problems such as adhesion to the material occur. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method of previously reducing calcium ion and magnesium ion described in JP-A-62-288,838 can be used very effectively. It is also effective to use water that has been sterilized in advance with a sterilizing agent such as sodium chlorinated isocyanurate. Further, in washing water, etc., isothiazolone compounds and siabendazoles described in JP-A-57-8,542, known chlorine-based bactericides, and other benzotriazoles, etc., Hiroshi Horiguchi "Chemistry of Antibacterial and Antifungal Agents"
(1986) Sankyo Publishing, Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982) Industrial Technology Association, Japan Society of Antimicrobial and Antifungal Activities, "Encyclopedia of Antimicrobial and Antifungal Agents" (1986) The bactericides described can also be used.

The washing water and the stabilizing solution have a pH of 4 to 9, preferably 5 to 8. Also, the temperature and time can be variously set depending on the characteristics of the photosensitive material, application, etc.
10 to 10 minutes at 5 to 45 ° C, preferably 25 to 40 ° C
The range of 15 seconds to 5 minutes is selected with. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilization treatment, all known methods described in JP-A-57-8543, JP-A-58-14834 and JP-A-60-220345 can be used.

In the stabilizing solution, compounds that stabilize the dye image, for example, benzaldehydes such as formalin and m-hydroxybenzaldehyde, formaldehyde bisulfite adducts, hexamethylenetetramine and its derivatives, hexahydrotriazine and its derivatives, N-methylol compounds such as dimethylol urea and N-methylol pyrazole, organic acids and pH buffering agents are included. The addition amount of these compounds is preferably 0.001 to 0.02 mol per liter of the stabilizing solution, but the lower the free formaldehyde concentration in the stabilizing solution is, the less the formaldehyde gas is scattered, which is preferable. From this point of view, examples of the dye image stabilizer include m-hydroxybenzaldehyde, hexamethylenetetramine, N-methylolpyrazole, N-methylolazoles described in JP-A-4-270344, N, N'-bi (1 , 2,4-Triazol-1-ylmethyl) piperazine, etc.
Azolylmethylamines described in 3753 are preferred.
Particularly, azoles such as 1,2,4-triazole described in JP-A-4-359249 (corresponding to European Patent Publication No. 519190A2) and 1,4-bis (1,2,4-triazol-1-ylmethyl). ) The combined use of azolylmethylamine and its derivatives such as piperazine is preferable because of high image stability and low formaldehyde vapor pressure.
In addition, if necessary, ammonium compounds such as ammonium chloride and ammonium sulfite, metal compounds such as Bi and Al, optical brighteners, hardeners, US Pat.
It is also preferable to contain an alkanolamine described in JP-A-6,583 or a preservative that can be contained in the fixing solution or the bleach-fixing solution, for example, a sulfinic acid compound described in JP-A No. 1-231051. .

The washing water and the stabilizing solution may contain various surfactants in order to prevent unevenness of water drops when the photosensitive material after processing is dried. Among these, it is preferable to use a nonionic surfactant, and an alkylphenol ethylene oxide adduct is particularly preferable. Octyl, nonyl, dodecyl and dinonylphenol are particularly preferable as the alkylphenol, and 8 to 14 are particularly preferable as the number of moles of ethylene oxide added. Further, it is also preferable to use a silicon-based surfactant having a high defoaming effect.

It is preferable to add various chelating agents to the washing water and the stabilizing solution. Preferred chelating agents include aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N, N'-trimethylenephosphonic acid and diethylenetriamine-N, N,
Examples thereof include organic phosphonic acids such as N ', N'-tetramethylenephosphonic acid, and hydrolyzates of maleic anhydride polymers described in European Patent 345,172A1.

The overflow solution resulting from the washing with water and / or the replenishment of the stabilizing solution can be reused in other steps such as the desilvering step. In the processing using an automatic processor, etc., when the above processing solutions are concentrated by evaporation,
In order to correct the concentration by evaporation, it is preferable to replenish an appropriate amount of water or a correction solution or a processing replenishing solution. The specific method for replenishing water is not particularly limited, but among them, a monitor water tank different from the bleaching tank described in JP-A-1-254959 and 1-254960 is installed, and water in the monitor water tank is installed. The amount of water vaporized in the bleaching tank is calculated from the amount of water vaporized in the bleaching tank, and the bleaching tank is replenished with water in proportion to the amount of water vaporized.
Nos. 3,249,644, 3,249,645, and 3,249,646, the evaporation correction method using a liquid level sensor and an overflow sensor are preferable.
As the water for correcting the evaporation of each treatment liquid, tap water may be used, but deionized water or sterilized water which is preferably used in the above washing step is preferably used.

Washing and / or stabilizing water treated with a reverse osmosis membrane can be effectively used. As the material of the reverse osmosis membrane, cellulose acetate, crosslinked polyamide, polyether, polysulfone, polyacrylic acid, polyvinylene carbonate, etc. can be used. The liquid feeding pressure in the use of these membranes is preferably ^{2 to} 10 kg / cm ² , and particularly preferably 3 to 7 kg / cm ^{2 because} of the stain prevention effect and the prevention of reduction of the amount of permeated water.

The treatment with the reverse osmosis membrane is preferably carried out on the water in the second tank and subsequent tanks for such multistage countercurrent washing and / or stabilization. Specifically, in the case of a two-tank configuration, the water in the second tank is treated and permeated with a reverse osmosis membrane in the second or third tank in the case of a three-tank configuration and the water in the third or fourth tank in a four-tank configuration. Same water tank (Tank for collecting water for reverse osmosis membrane treatment; hereinafter referred to as “collection tank”)
Alternatively, it is carried out by returning to a washing and / or stabilizing tank located thereafter. Furthermore, concentrated washing and /
Alternatively, one of the measures is to return the stabilizing solution to the bleach-fixing bath upstream of the sampling tank.

Various treatment liquids are preferably used at 10 ° C to 50 ° C. Normally, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature accelerates the processing to shorten the processing time, and a lower temperature lowers the image quality to improve the stability of the processing liquid. be able to.

Each processing solution can be commonly used for processing two or more kinds of photosensitive materials. For example, by treating the color negative film and the color paper with the same treatment liquid, it is possible to reduce the cost of the processor and simplify the treatment.

The present invention can be applied to various color light-sensitive materials such as color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers. In addition, Japanese Examined Patent Publication 2-32615 and Actual Examination 3-39784
It is also suitable for the lens-fitted film unit described in.

The photosensitive material may have at least one photosensitive layer provided on a support. As a typical example, a silver halide photographic light-sensitive material having on a support at least one light-sensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. Is. The photosensitive layer is a unit photosensitive layer having a color sensitivity to any of blue light, green light, and red light. In a light-sensitive material for photographing a multilayer silver halide color photograph, the unit photosensitive layer is generally used. The arrangement is such that the red-sensitive layer, the green-sensitive layer and the blue-sensitive layer are arranged in this order from the support side. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers. A non-photosensitive layer may be provided between the above-described silver halide photosensitive layers and as the uppermost layer and the lowermost layer. These may contain a coupler, a DIR compound, a color mixing inhibitor, etc. described later. The plural silver halide emulsion layers constituting each unit photosensitive layer are composed of two layers, a high-sensitivity emulsion layer and a low-sensitivity emulsion layer, as described in DE 1,121,470 or GB 923,045.
It is preferable to arrange them so that the photosensitivity becomes lower toward the support. Further, JP-A-57-112751, 62-200350,
As described in JP-A Nos. 62-206541 and 62-206543, a low-sensitivity emulsion layer may be provided on the side farther from the support and a high-sensitivity emulsion layer may be provided on the side closer to the support. As a specific example, from the side farthest from the support, low-sensitivity blue photosensitive layer (BL) / high-sensitivity blue photosensitive layer (BH) / high-sensitivity green photosensitive layer (GH) / low-sensitivity green photosensitive layer (GL) / High-sensitivity red photosensitive layer (RH) / Low-sensitivity red photosensitive layer (RL), or BH / BL / GL / GH / RH / RL, or BH / BL / GH / GL / RL / RH It can be installed in the order of. Further, as described in JP-B-55-34932, from the side farthest from the support, the blue-sensitive layer / GH / RH / GL
It can also be arranged in the order of / RL. In addition, JP-A-56-2573
8 and 62-63936, the blue-sensitive layer / GL / RL / GH / RH may be arranged in this order from the side farthest from the support.

As described in JP-B-49-15495, the upper layer is a silver halide emulsion layer having the highest sensitivity, the middle layer is a silver halide emulsion layer having a lower sensitivity, and the lower layer is a layer more sensitive than the middle layer. An arrangement may be mentioned in which a silver halide emulsion layer having a low photosensitivity is arranged and three layers having different sensitivities are sequentially lowered toward the support. Even when it is composed of three layers having different sensitivities, the method of
As described in 59-202464, in the same color-sensitive layer, a medium-speed emulsion layer / high-speed emulsion layer / low-speed emulsion layer may be arranged in this order from the side remote from the support. Other,
They may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer. Also, in the case of four or more layers, the arrangement may be changed as described above. To improve color reproducibility, US
4,663,271, 4,705,744, 4,707,436, JP-A-62-1
60448, 63-89850, and a donor layer (CL) having a multilayer effect, which has a spectral sensitivity distribution different from that of the main photosensitive layer such as BL, GL, and RL, is arranged adjacent to or in proximity to the main photosensitive layer. Is preferred.

In a general light-sensitive material for printing (color photographic paper), silver halide emulsion grains are spectrally sensitized by the blue-sensitive, green-sensitive and red-sensitive spectral sensitizing dyes in the order of the above-mentioned color forming layers. It can be formed by coating on a support in the order described above. However, the order may be different from this. In other words, from the viewpoint of rapid processing, it is preferable that the photosensitive layer containing the largest silver halide grains having the average grain size comes to the uppermost layer, or from the viewpoint of storage stability under light irradiation, the lowermost layer is the magenta color photosensitive layer. In some cases it may be preferable to do so. Further, the light-sensitive layer and the color-developing hue may not have the above correspondence, and at least one infrared-sensitive silver halide emulsion layer can be used.

A preferred silver halide used in a photographic light-sensitive material is a silver iodobromide containing about 30 mol% or less of silver iodide,
It is silver iodochloride or silver iodochlorobromide. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide. Silver halide grains in photographic emulsions have regular crystals such as cubes, octahedra and tetradecahedrons, grains having irregular crystal forms such as spheres and plates, twin planes, etc. It may have a crystal defect of, or a composite form thereof. The grain size of the silver halide may be fine grains of about 0.2 μm or less or large grains having a projected area diameter of up to about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion. Dispersion coefficient 15% or less, 1
Monodisperse particles of 0% or less are preferable. Silver halide photographic emulsions are, for example, Research Disclosure (hereinafter,
(Abbreviated as RD) No. 17643 (December 1978), pp. 22-23,
"I. Emulsion preparation and type
s) ”and ibid. No. 18716 (November 1979), p. 648,
It can be prepared using the method described in the same No. 307105 (November 1989), pages 863-865 and the like.

Further, tabular grains having an aspect ratio of about 3 or more can be used in the present invention. Tabular grains are described in Gutoff, Photographic Science and Engineering (Gutoff, Photographic Science and E).
14: 248-257 (1970), US 4,43
It can be easily prepared by the method described in 4,226, GB 2,112,157. The crystal structure may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. Silver halides having different compositions may be joined by epitaxial joining, and may be joined with a compound other than silver halide such as silver rhodanide and lead oxide. Also, a mixture of particles having various crystal forms may be used. The above emulsion may be either a surface latent image type which forms a latent image mainly on the surface, an internal latent image type which is formed inside the grain or a type which has a latent image both on the surface and inside, but a negative type emulsion. It is necessary to be.
Among the internal latent image type emulsions, core / shell type internal latent image type emulsions described in JP-A-63-264740 may be used, and the preparation method thereof is described in JP-A-59-133542. The thickness of the shell of this emulsion varies depending on development processing and the like, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

The silver halide emulsion is usually one which has been physically ripened, chemically ripened and spectrally sensitized. Additives used in such a process are described in RD17643, RD 18716 and RD 307105, and the corresponding portions are summarized in the table below. In the light-sensitive material of the present invention, two or more kinds of emulsions having different characteristics of at least one of the grain size, grain size distribution, halogen composition, grain shape, and sensitivity of the photosensitive silver halide emulsion are mixed in the same layer. Can be used. US Pat. No. 4,082,553, the surface of which has been fogged, the silver halide particles, US 4,626,498, JP-A-59-214852, the inside of which has been fogged the silver halide particles, and colloidal silver as a photosensitive silver halide emulsion layer and It is / or preferably applied to a substantially light-insensitive hydrophilic colloid layer. The fogged silver halide grain inside or on the surface means a silver halide grain capable of developing uniformly (non-imagewise) regardless of the unexposed portion and exposed portion of the light-sensitive material. . The silver halide forming the inner core of a core / shell type silver halide grain having a fogged inside may have a different halogen composition. Examples of the silver halide whose inside or surface is fogged include silver chloride, silver chlorobromide,
Both silver iodobromide and silver chloroiodobromide can be used. The average grain size of these fogged silver halide grains is preferably 0.01 to 0.75 .mu.m, more preferably 0.05 to 0.6 .mu.m. The grain shape may be regular grain or polydisperse emulsion, but monodisperse grain is preferable.

It is also possible to use non-photosensitive fine grain silver halide. Non-photosensitive fine grain silver halide is silver halide fine grains that are not exposed during imagewise exposure to obtain a dye image and are not substantially developed in the developing process, and are preferably not fogged in advance. . Fine grain silver halide has a silver bromide content of 0 to 10
It is 0 mol% and may contain silver chloride and / or silver iodide, if necessary. Preferred is one containing 0.5 to 10 mol% of silver iodide. Fine grain silver halide has an average grain size (average diameter of circles equivalent to the projected area) of 0.01 to 0.5μ.
m is preferable, and 0.02 to 0.2 μm is more preferable. The fine grain silver halide does not need to be optically sensitized nor spectrally sensitized. However, prior to adding this to the coating liquid, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, mercapto-based compound or zinc compound in advance. Colloidal silver can be contained in the fine silver halide grain-containing layer. The silver coating amount of the photosensitive material for photography is preferably 6.0 g / m ² or less, and 4.5 g / m ²
The following are the most preferable.

In the light-sensitive material for printing, it is preferable to use silver chloride, silver chlorobromide or silver chloroiodobromide grains having silver chloride of 95 mol% or more as silver halide grains. In particular, in order to accelerate the development processing time, a silver chlorobromide or silver chloride containing substantially no silver iodide can be preferably used. The term "substantially free of silver iodide" as used herein means that the silver iodide content is 1 mol% or less, preferably 0.2 mol% or less. On the other hand, for the purpose of enhancing high illuminance sensitivity, spectral sensitization sensitivity, or enhancing stability over time of a light-sensitive material, 0.01 to 3 mol% on the emulsion surface as described in JP-A-3-84545. In some cases, high silver chloride grains containing silver iodide are preferably used. The halogen composition of the emulsion may be different or the same between grains, but if an emulsion having the same halogen composition among grains is used, it is easy to make the properties of each grain uniform. Regarding the halogen composition distribution inside the silver halide emulsion grains, the so-called uniform structure grains having the same composition in any part of the silver halide grains, or the core inside the silver halide grains and the shell surrounding it. (shell)
Particles having a so-called laminated structure having a different halogen composition with [one or more layers], or a structure having a portion having a different halogen composition in a non-layer form inside or on the surface of the particle (edges, corners or surfaces of the particles when present on the surface of the particle) Particles having a structure in which portions having different compositions are bonded to each other can be appropriately selected and used. In order to obtain high sensitivity, it is advantageous to use either of the latter two rather than the particles having a uniform structure, and it is also preferable from the viewpoint of pressure resistance. When the silver halide grains have the above structure, the boundary between different portions in the halogen composition is an unclear boundary because a mixed crystal is formed due to the composition difference even if the boundary is clear. Alternatively, it may be one that positively has a continuous structural change.

The high silver chloride emulsion preferably has a structure having a localized silver bromide phase in the inside and / or on the surface of the silver halide grain in the form of layer or non-layer as described above. The halogen composition of the localized phase preferably has a silver bromide content of at least 10 mol%, and preferably 20 mol%.
It is more preferable that the number exceeds. These localized phases can be present inside the particles, on the edges, corners, or on the surface of the particles, and one preferable example thereof is that epitaxially grown on the corners of the particles. It is also effective to further increase the silver chloride content of the silver halide emulsion for the purpose of reducing the replenishment amount of the developing solution. In such a case, the silver chloride content is 9
An emulsion of substantially pure silver chloride such as 8 mol% to 100 mol% is also preferably used.

Average grain size of silver halide grains contained in the silver halide emulsion (the grain size is determined by the diameter of a circle equivalent to the projected area of the grain, and the number average thereof is taken).
Is preferably 0.1 μm to 2 μm. Further, the particle size distribution thereof is preferably a so-called monodisperse coefficient of variation of 20% or less (standard deviation of particle size distribution divided by average particle size), preferably 15% or less, more preferably 10% or less. . At this time, for the purpose of obtaining a wide latitude, it is also preferable to use the above monodispersed emulsion by blending it in the same layer, or to perform multi-layer coating. The shape of silver halide grains contained in a photographic emulsion is one having a regular crystal form such as a cube, a tetradecahedron or an octahedron, an irregular shape such as a sphere or a plate.
Those having a gular) crystal form or those having a composite form thereof can be used. It may also be a mixture of materials having various crystal forms. In the present invention, it is preferable that 50% or more, preferably 70% or more, and more preferably 90% or more of the particles having the above-mentioned regular crystal form are contained in the present invention. In addition to these, an emulsion in which tabular grains having an average aspect ratio (diameter in terms of circle / thickness) of 5 or more, preferably 8 or more exceeds 50% of all grains as a projected area can also be preferably used.

The localized phase of the silver halide grain or its substrate may contain a different metal ion or its complex ion. Preferred metals include Group VIII and Group VIII of the Periodic Table.
It is selected from a metal ion or a metal complex belonging to the IIb group, a lead ion, and a thallium ion. Ions or their complex ions mainly selected from iridium, rhodium, iron etc. in the localized phase, and metal ions selected mainly from osmium, iridium, rhodium, platinum, ruthenium, palladium, cobalt, nickel, iron etc. as the substrate. Alternatively, the complex ions can be used in combination. Further, the type and concentration of the metal ion can be changed depending on the localized phase and the substrate. Plural kinds of these metals may be used. In particular, iron and iridium compounds are preferably present in the silver bromide localized phase.

These metal ion-providing compounds are used in a gelatin aqueous solution which becomes a dispersion medium when silver halide grains are formed,
Of the silver halide grains of the present invention by means such as adding in an aqueous solution of a halide, in an aqueous solution of silver salt or other aqueous solution, or in the form of silver halide fine particles containing metal ions in advance and dissolving the fine particles. It is contained in the localized phase and / or other particle portion (matrix). The metal ions used in the present invention can be contained in the emulsion grains either before, during or immediately after grain formation. This can be changed depending on the position of the metal ion contained in the particle.

The silver halide emulsion is usually chemically and spectrally sensitized. Regarding the chemical sensitization method, chemical sensitization using a chalcogen sensitizer (specifically, sulfur sensitization represented by the addition of an unstable sulfur compound, selenium sensitization with a selenium compound, tellurium sensitization with a tellurium compound is performed. Noble metal sensitization typified by gold sensitization, reduction sensitization and the like can be used alone or in combination. Regarding compounds used for chemical sensitization, see Japanese Patent Application Laid-Open No.
Those described in the lower right column of page 18 to the upper right column of page 22 of JP-A 2-215272 are preferably used. The effect of the constitution of the light-sensitive material of the present invention is more remarkable than when the gold-sensitized high silver chloride emulsion is used. The emulsion used in the present invention is a so-called surface latent image type emulsion in which a latent image is mainly formed on the grain surface.

Various compounds or their precursors are added to the silver halide emulsion for the purpose of preventing fog during the production process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. You can As specific examples of these compounds, those described on pages 39 to 72 of the above-mentioned JP-A No. 62-215272 are preferably used. Further, a 5-arylamino-1,2,3,4-thiatriazole compound described in EP 0447647 (wherein the aryl residue has at least one electron-withdrawing group) is also preferably used.

Spectral sensitization is carried out for the purpose of imparting spectral sensitivity in a desired light wavelength region to the emulsion of each layer in the light-sensitive material. Examples of spectral sensitizing dyes used for spectral sensitization in the blue, green, and red regions include FM Harmer's Heterocyclic co
mpounds-Cyanine dyes and related compounds (John W
iley & Sons New York, London, 1964). Examples of specific compounds and the spectral sensitization method are described in the above-mentioned JP-A-62-21.
Those described on page 22, upper right column to page 38 of Japanese Patent No. 5272 are preferably used. Further, as the red-sensitive spectral sensitizing dye for silver halide emulsion grains having a particularly high silver chloride content, the spectral sensitizing dye described in JP-A-3-123340 is stable, has strong adsorption, and has an exposure temperature. It is very preferable from the viewpoint of dependency.

For efficient spectral sensitization in the infrared region, JP-A-3-15049, page 12, upper left column to page 21, lower left column, or JP-A-3-20730, page 4, lower left column to page 15, lower left column, European Patent EP0. , 420, 011 page 4, lines 21-6
Page 54 line, EP 0,420,012, page 4, 12
Lines-10 pages 33 lines, European patent EP 0,443,466
And the sensitizing dyes described in US Pat. No. 4,975,362 are preferably used.

The timing of adding these spectral sensitizing dyes to the emulsion may be any stage of emulsion preparation known to be useful so far. In other words, before preparing the silver halide emulsion grains, during grain formation, immediately after grain formation, before entering the washing step, before chemical sensitization, during chemical sensitization, immediately after chemical sensitization, until the emulsion is cooled and solidified. You can choose from either. Most commonly, it is carried out after the completion of chemical sensitization and before the application, but is described in US Pat.
It is also possible to add spectral sensitization simultaneously with chemical sensitization by adding it at the same time as the chemical sensitizer as described in JP-A No. 628969 and No. 4225666.
It can be carried out prior to chemical sensitization as described in No. 28, or it can be added before the completion of silver halide grain precipitation to initiate spectral sensitization. It is also possible to add the spectral sensitizing dyes separately, as taught in U.S. Pat. No. 4,225,666, i.e. adding some prior to chemical sensitization and the rest after chemical sensitization. It is possible and can be at any time during silver halide grain formation, including the method taught in US Pat. No. 4,183,756. Of these, it is particularly preferable to add a sensitizing dye before the step of washing the emulsion with water or before the chemical sensitization.

The addition amount of these spectral sensitizing dyes is wide depending on the case, and is 0.5 per mol of silver halide.
The range of × 10 ^-6 mol to 1.0 × 10 ^-2 mol is preferable.
More preferably, 1.0 × 10 ^-6 mol to 5.0 × 10 ^-3
It is in the molar range. In the present invention, particularly when a sensitizing dye having a spectral sensitizing sensitivity in the red region to the infrared region is used, the compounds described in JP-A-2-157749, page 13, lower right column to page 22, lower right column, may be used in combination. preferable. By using these compounds, the storability and processing stability of the light-sensitive material and the supersensitizing effect can be specifically enhanced. Above all, it is particularly preferable to use the compounds of the general formulas (IV), (V) and (VI) in the same patent in combination. These compounds are used in an amount of 0.5 × 10 ^-5 mol to 1 mol of silver halide.
5.0 × 10 ⁻² mol, preferably 5.0 × 10 ⁻⁵ mol
An amount of 5.0 × 10 ⁻³ mol is used, and 0.1 times to 10000 times, preferably 0.5 times to 5 times per mol of the sensitizing dye.
There is an advantageous usage amount in the range of 000 times.

In the light-sensitive material, a hydrophilic colloid layer is used for the purpose of preventing irradiation and halation and improving safety of safelight, etc., and European Patent EP03374.
Dyes which can be decolorized by treatment (in particular, oxonol dyes and cyanine dyes) described on pages 27 to 76 of the specification of 90A2 can be added. Some of these water-soluble dyes deteriorate the color separation and safelight safety when the amount used is increased. As the dyes that can be used without deteriorating the color separation, the water-soluble dyes described in Japanese Patent Application No. 03-310143, Japanese Patent Application No. 03-310189 and Japanese Patent Application No. 03-310139 are preferable.

Instead of the water-soluble dye or in combination with the water-soluble dye, a colored layer which can be decolorized by treatment is used. The coloring layer that can be decolorized by the treatment used may be in direct contact with the emulsion layer, or may be disposed so as to be in contact with the emulsion layer via an intermediate layer containing a treatment color mixing inhibitor such as gelatin or hydroquinone. This colored layer is preferably provided in the lower layer (support side) of the emulsion layer that develops a primary color of the same kind as the colored color. It is possible to install all the colored layers corresponding to each primary color individually, or to selectively install only a part of them. It is also possible to provide a colored layer that is colored corresponding to a plurality of primary color gamuts. The optical reflection density of the colored layer is the wavelength range used for exposure (visible light range of 400 nm to 700 nm in normal printer exposure, wavelength of scanning exposure light source used in scanning exposure).
It is preferable that the optical density value at the wavelength having the highest optical density is 0.2 or more and 3.0 or less. More preferably 0.5 to 2.5, especially 0.8 to 2.0
The following are preferred.

A conventionally known method can be applied to form the colored layer. For example, Japanese Patent Laid-Open No. 2-282244-3
The dyes described on page 8 from the upper right column of the page, and JP-A-3-79
No. 31, page 3, upper right column to page 11, lower left column, a method of incorporating a solid fine particle dispersion in a hydrophilic colloid layer, a method of mordanting an anionic dye with a cationic polymer, a method of halogenating the dye Examples thereof include a method of adsorbing to fine particles such as silver and fixing in a layer, a method of using colloidal silver as described in JP-A-1-239544, and the like. As a method for dispersing a fine powder of a pigment in a solid state, for example, a method of containing a fine powder dye which is substantially water-insoluble at a pH of 6 or lower but is substantially water-soluble at a pH of 8 or higher is disclosed in Japanese Patent Laid-Open No. 2-30824
No. 4, pages 4-13. Also, for example,
A method of mordanting an anionic dye on a cationic polymer is described in JP-A-2-84637, pages 18 to 26. For the preparation method of colloidal silver as a light absorber, see US Pat. Nos. 2,688,601 and 3,45.
No. 9,563. Among these methods, the method of incorporating a fine powder dye and the method of using colloidal silver are preferable.

As the binder or protective colloid that can be used in the light-sensitive material, it is advantageous to use gelatin, but other hydrophilic colloids can be used alone or together with gelatin. As a preferable gelatin, it is preferable to use low calcium gelatin having a calcium content of 800 ppm or less, more preferably 200 ppm or less. Further, in order to prevent various molds and bacteria which propagate in the hydrophilic colloid layer and deteriorate the image, it is preferable to add an antifungal agent as described in JP-A-63-271247.

When exposing the photosensitive material for printing to the printer, it is preferable to use the band stop filter described in US Pat. No. 4,880,726. As a result, light color mixture is removed, and color reproducibility is significantly improved. The exposed light-sensitive material may be subjected to a conventional color development process, but for the purpose of rapid processing, it is preferable to carry out a bleach-fixing process after color development. Particularly when the above high silver chloride emulsion is used, the pH of the bleach-fixing solution is preferably about 6.5 or less, more preferably about 6 or less for the purpose of promoting desilvering.

The photographic additives that can be used are also described in RD, and the relevant portions are described in the table below. Types of additives RD17643 RD18716 RD307105 1. Chemical sensitizer page 23 page 648 page right column page 866 2. Sensitivity enhancer 648 page right column 3. Spectral sensitizer, pages 23 to 24 page 648 right column 866 to 868 supersensitizer to page 649 right column 4. Whitening agent page 24 647 right column 868 page 5 Light absorber, pages 25 to 26, page 649, right column, page 873, filter, page 650, left column, dye, ultraviolet absorber 6. Binder, page 26, page 651, left column 873 to 874, page 7. Plasticizer, page 27, page 650, right Column 876 Lubricants 8. Coating aids, 26-27 Pages 650 Right column 875-876 Pages Surfactant 9. Static 27 pages 650 Page right columns 876-877 Inhibitors 10. Matting agents 878-879

Although various dye-forming couplers can be used in the light-sensitive material, the following couplers are particularly preferable. Yellow couplers: couplers represented by formulas (I) and (II) of EP 502,424A; couplers represented by formulas (1) and (2) of EP 513,496A (particularly Y-28 on page 18); Japanese Patent Application No. 4 Claim 1 of -134523
A coupler represented by the general formula (I) in US Pat. No. 5,066,576, column 1, lines 45 to 55;
Coupler represented by the general formula (I) in paragraph 0008 of JP-A-4-274425; coupler described in claim 1 on page 40 of EP 498,381A1 (particularly D-35 on page 18); formula on page 4 of EP 447,969A1 (Y)
A coupler represented by (particularly Y-1 (page 17), Y-54 (page 41));
Couplers represented by formulas (II) to (IV) on lines 36 to 58 of column 7, US 4,476,219 (especially II-17,19 (column 17), II-24 (column 19)). Acyl acetanilide type coupler, among others,
Pivaloyl acetanilide type coupler having a halogen atom or an alkoxy group at the ortho position of the anilide ring, European Patent No. EP 044969A, JP-A-5-107701.
And the acyl group described in JP-A-5-113642 and the like are 1
Acylacetanilide type coupler having a position-substituted cycloalkanecarbonyl group, European Patent EP-0482552
Malondianilide type couplers described in No. A and EP-0524540A.

Magenta coupler; JP-A-3-39737 (L-57 (1
Page 1 (bottom right), L-68 (page 12 bottom right), L-77 (page 13 bottom right); EP 456,
257, A-4 -63 (page 134), A-4 -73, -75 (page 139); EP 486,
965 M-4, -6 (26 pages), M-7 (27 pages); Japanese Patent Application No. 4-234120, paragraph 0
024 of M-45; Japanese Patent Application No. 4-36917, paragraph 0036 of M-1; JP-A-4-36
As an M-22.5-pyrazolone magenta coupler according to paragraph 0237 of 2631, WO92 / 18901 and WO92 / 18901
Arylthio-eliminating 5-pyrazolone-based magenta couplers described in WO92 / 18902 and WO92 / 18903. As a pyrazoloazole type coupler, JP-A-61-
Pyrazoloazole couplers containing sulfonamide groups in the molecule as described in JP-A-65246, JP-A-61-
Pyrazoloazole couplers having an alkoxyphenyl sulfonamide ballast group as described in 147254, and European Patent Nos. 226,849A and 294,7.
A pyrazoloazole coupler having an alkoxy group or an aryloxy group at the 6-position as described in No. 85A.

Cyan coupler: CX-1, JP-A-4-204843
3,4,5,11,12,14,15 (pages 14 to 16); C-7,1 of JP-A-4-43345.
0 (page 35), 34, 35 (page 37), (I-1), (I-17) (pages 42 to 43); general formula (Ia) or (of claim 1 of Japanese Patent Application No. 4-236333. A coupler represented by Ib). Polymer coupler: JP-A-2-44345, P-1, P-5 (page 11).
Phenol-based couplers and naphthol-based couplers, diphenylimidazole-based cyan couplers described in JP-A-2-33144, 3-hydroxypyridine-based cyan couplers described in European Patent EP 0333185A2, and JP-A-64-32260. Cyclic active methylene cyan couplers described, European patent EP04562
26A1 specification, pyrrolopyrazole type cyan coupler, European Patent EP0484909, pyrroloimidazole type cyan coupler, European Patent EP0488.
The pyrrolotriazole type cyan couplers described in 248 and EP 0491197A1.

As couplers in which the color forming dye has a suitable diffusibility, US 4,366,237, GB 2,125,570, EP 96,873B,
Those described in DE 3,234,533 are preferred. The coupler for correcting the unwanted absorption of the color forming dye is a yellow-colored cyan coupler represented by the formulas (CI), (CII), (CIII) and (CIV) described on page 5 of EP 456,257A1 (especially on page 84). YC-86), the EP
Yellow colored magenta coupler ExM-7 (202
Page), EX-1 (page 249), EX-7 (page 251), magenta colored cyan coupler CC-9 (column 8) described in US 4,833,069,
CC-13 (column 10), US 4,837,136 (2) (column 8), WO92
The colorless masking couplers of formula (A) in claim 1 of / 11575 (in particular the exemplified compounds on pages 36 to 45) are preferred. Examples of the compound (including a coupler) which reacts with an oxidized product of a developing agent to release a photographically useful compound residue include the following. Development inhibitor releasing compound: EP 378,2
Compounds represented by formulas (I), (II), (III), and (IV) described on page 11 of 36A1 (particularly T-101 (page 30), T-104 (page 31), T-113 (36 page),
T-131 (page 45), T-144 (page 51), T-158 (page 58)), EP436, 938A2
On page 7 of the formula (I) compound (especially D-49 (5
1)), a compound represented by the formula (1) of Japanese Patent Application No. 4-134523 (particularly (23) of paragraph 0027), the formulas (I), (II), described on pages 5 to 6 of EP 440,195A2. Compound represented by (III) (especially on page 29)
I- (1)); Bleach accelerator releasing compounds: compounds represented by formulas (I) and (I ') on page 5 of EP 310,125A2 (particularly (60) and (6 on page 61)
1)) and a compound represented by the formula (I) in claim 1 of Japanese Patent Application No. 4-325564 (particularly (7) in paragraph 0022); a ligand-releasing compound: represented by LIG-X described in claim 1 of US 4,555,478. Compounds (especially compounds on lines 21 to 41 of column 12); Leuco dye releasing compounds: compounds 1 to 6 of columns 3 to 8 of US 4,749,641; fluorescent dye releasing compounds: represented by COUP-DYE of claim 1 of US 4,774,181 Compounds (especially columns 7-10)
Compounds 1 to 11); development accelerator or fogging agent releasing compounds: compounds represented by formulas (1), (2) and (3) of column 3, US Pat. No. 4,656,123 (particularly (I-22) of column 25) and EP 450,6
ExZK-2, 37A2, page 75, lines 36-38; compounds that release a dye group only upon leaving: a compound of formula (I) in claim 1 of US 4,857,447 (especially Y- in columns 25-36). 1 ~
Y-19).

As the additives other than the coupler, the following are preferable. Dispersion medium for oil-soluble organic compound: JP-A-62-2
15272 P-3,5,16,19,25,30,42,49,54,55,66,81,85,86,
93 (pages 140 to 144); Latex for impregnation of oil-soluble organic compounds: Latex described in US 4,199,363; Oxidized developer scavenger: US 4,978,606, column 2, lines 54 to 62, compound represented by formula (I) ( Especially I-, (1), (2), (6), (12)
(Columns 4-5), US 4,923,787, column 2, lines 5-10 (particularly compound 1 (column 3); stain inhibitor: EP
298321A, page 4, lines 30-33, formulas (I)-(III), especially I-47,72,
III-1,27 (pp. 24-48); Anti-fading agent: A-6,7 of EP 298321A.
20,21,23,24,25,26,30,37,40,42,48,63,90,92,94,164 (6
Pp. 9-118), US 5,122,444, columns 25-38, II-1 to III-
23, especially III-10, EP 471347A, pages 1-12, I-1 to III-4,
II-2, US 5,139,931 columns 32-40, A-1 to 48, especially A-39,42; to reduce the use of color enhancers or color inhibitors Materials: EP 411324A, pages 5 to 24 I-1 to II-15, especially
I-46; Formalin Scavenger: EP 477932A 24-29
SCV-1 to 28, especially SCV-8; Hardener: JP-A 1-214845
Formulas in columns 13-23 of H-1,4,6,8,14, US 4,618,573 on page 17
Compounds (H-1 to 54) represented by (VII) to (XII), JP-A-2-
214852, page 8, lower right, compound represented by formula (6) (H-1 to 7
6), especially the compound described in claim 1 of H-14, US 3,325,287; Development inhibitor precursor: P-2 of JP-A-62-168139
4,37,39 (pages 6 to 7); Compounds as claimed in claim 1, US 5,019,492, in particular column 7, 28,29; preservatives, fungicides: US
4,923,790 columns 3 to 15 I-1 to III-43, especially II-1,9,
10,18, III-25; Stabilizers, antifoggants: US 4,923,793 columns 6-16 I-1 to (14), especially I-1,60, (2), (13), US
4,952,483 columns 25-32 compounds 1-65, especially 36: chemical sensitizer: triphenylphosphine selenide, JP
-40324 Compound 50; Dye: JP-A-3-156450, pages 15-18, a-1 to b-20, especially a-1,12,18,27,35,36, b-5,27 to 29 V-1 to 23, especially V-1, EP 445627A, FI-1 on pages 33 to 55
-F-II-43, especially FI-11, F-II-8, EP 457153A, pages 17-28, III-1 to 36, especially III-1,3, WO 88/04794, 8 to 26 Dy
microcrystalline dispersions of e-1 to 124, compounds 1 to 22 of EP 319999A, pages 6 to 11, especially compound 1, formula (1) to EP 519306A
Compound D-1 to 87 represented by (3) (pages 3 to 28), US 4,268,62
Compounds 1 to 22 represented by the formula (I) of 2 (columns 3 to 10),
Compounds (1) to (31) represented by the formula (I) of US 4,923,788
(Columns 2 to 9); UV absorber: Compounds (18b) to (18r), 101 to 427 (pages 6 to 9) represented by formula (1) of JP-A-46-3335,
Compounds (3) to (66) (10) represented by formula (I) of EP 520938A
~ 44) and the compound of formula (III) HBT-1 to 10 (1
(Page 4), compound (1) represented by formula (1) of EP 521823A
(31) (columns 2-9).

The support used for the light-sensitive material for printing may be any support such as glass, paper and plastic film as long as it can be coated with a photographic emulsion layer, but the most preferred is a reflection type support. The "reflective support" used in the present invention refers to one which enhances the reflectivity to make the dye image formed on the silver halide emulsion layer clear, and such a reflective support is a support. Those coated with a hydrophobic resin containing a light-reflecting substance such as titanium oxide, zinc oxide, calcium carbonate, or calcium sulfate dispersed therein, or those using the hydrophobic resin itself containing a dispersed light-reflecting substance as a support. Is included. For example polyethylene coated paper,
Polyethylene terephthalate-coated paper, polypropylene-based synthetic paper, a transparent support provided with a reflective layer or used in combination with a reflective material, for example, glass plate, polyethylene terephthalate, polyester film of cellulose triacetate or cellulose nitrate, polyamide film, polycarbonate There are films, polystyrene films, vinyl chloride resins, etc. The reflective support used in the present invention is a paper support whose both surfaces are coated with a water resistant resin layer,
It is preferable that at least one of the waterproof resin layers contains fine white pigment particles.

The water-resistant resin of the reflective support is a resin having a water absorption rate (% by weight) of 0.5, preferably 0.1 or less, and examples thereof include polyolefins such as polyethylene, polypropylene and polyethylene-based polymers, vinyl polymers and the like. The copolymer (polystyrene, polyacrylate and its copolymer), polyester (polyethylene terephthalate, polyethylene isophthalate etc.) and its copolymer. Polyethylene and polyester are particularly preferable. As the polyethylene, high density polyethylene, low density polyethylene, linear low density polyethylene and blends of these polyethylenes can be used. The melt flow rate (hereinafter abbreviated as MFR) before processing of these polyethylene resins is preferably 1.2 g / 10 minutes to 12 g / 10 minutes in a value measured under condition 4 of JIS K 7210, Table 1. The MFR of the polyolefin resin before processing referred to here is the M of the resin before kneading the bluing agent and the white pigment.
Indicates FR.

The weight ratio of the water resistant resin to the white pigment is 98/2 to 30/70 (water resistant resin / white pigment), preferably 95/5 to 50/50, particularly preferably 90/10. It is 60/40. 2% by weight of white pigment
If it is less than 70% by weight, the contribution to whiteness is insufficient, and if it exceeds 70% by weight, the surface smoothness of the photographic support is insufficient, and a photographic support having excellent glossiness is obtained. I can't. These water resistant resin layers are 2 to 200
It is preferable to coat the substrate with a thickness of μm, and more preferably 5 to 80 μm. If it is thicker than 200 μm, the brittleness of the resin is emphasized, causing physical problems such as cracking. When the thickness is less than 2 μm, the original waterproofing property of the coating is impaired, the whiteness and the surface smoothness cannot be satisfied at the same time, and the physical properties become too soft, which is not preferable. The thickness of the resin or resin composition with which the surface of the substrate other than the photosensitive layer-coated surface is coated is 5 to 100.
μm is preferable, and more preferably 10 to 50 μm. When the thickness exceeds this range, the brittleness of the resin is emphasized, and problems such as cracking occur in physical properties. If it is less than this range, the waterproof property which is the original purpose of the coating is impaired and the physical properties become too soft, which is not preferable.

In the reflective support, the water-resistant resin coating layer on the photosensitive layer coating side is a reflective support comprising two or more water-resistant resin coating layers having different contents of white pigments. In some cases, it may be more preferable from the viewpoint of production suitability and the like. In this case, among the water-resistant resin coating layers having different white pigment contents, the white pigment content of the water-resistant resin coating layer closest to the substrate is at least one of the water-resistant resin coating layers above this layer. It is preferably lower than the content of the white pigment. As a further preferred embodiment, among the water resistant resin coating layers having different contents of white pigment of the reflective support, the reflective support having the highest content of white pigment of the water resistant resin coating layer closest to the photosensitive layer, or the reflective support The support is composed of at least three water-resistant resin coating layers, and any one of intermediate layers other than the water-resistant resin coating layer closest to the photosensitive layer of the multi-layer water-resistant resin layer and the substrate. The reflective support has the highest content of the white pigment in.

The content of the white pigment in each layer in the multilayer waterproof resin layer is 0% by weight to 70% by weight, preferably 0% by weight.
˜50% by weight, more preferably 0% to 40% by weight. The content of the layer having the highest content of white pigment in the multilayer waterproof resin layer is 9% by weight to 70% by weight, preferably 15% by weight to 50% by weight, and more preferably 20% by weight to 40% by weight. Is. If the content of the white pigment in this layer is less than 9% by weight, the sharpness of the image is low, and if it exceeds 70% by weight, the melt-extruded film is cracked. The thickness of each layer of the multilayer waterproof resin layer is 0.5 μm to 5 μm.
0 μm is preferable. For example, in the case of a multilayer waterproof resin layer having a two-layer structure, the thickness of each layer is preferably 0.5 μm to 50 μm, and the total thickness of the layers combined is in the range (2 to 200).
μm) is preferable. In the case of a three-layer structure, the uppermost layer has a thickness of 0.5 μm to 10 μm, and the intermediate layer has a thickness of 5 μm.
˜50 μm, the thickness of the lower layer (layer closest to the substrate) is 0.5
It is preferably 10 μm. The film thickness of the top and bottom layers is 0.5
When it is at most μm, die lip streaks are likely to occur due to the action of the highly filled white pigment in the intermediate layer. On the other hand, if the thickness of the uppermost layer and the lowermost layer, especially the uppermost layer, is 10 μm or more, the sharpness is lowered.

It is preferable that the white pigment fine particles are uniformly dispersed in the reflective layer without forming aggregates of particles.
The size of the distribution can be obtained by measuring the occupied area ratio (%) (Ri) of the fine particles projected on the unit area. The variation coefficient of the occupied area ratio (%) can be obtained by the ratio s / R of the standard deviation s of Ri to the average value (R) of Ri. In the present invention, the coefficient of variation of the occupied area ratio (%) of the fine particles of the pigment is preferably 0.15 or less, more preferably 0.12 or less. 0.08 or less is particularly preferable. A support having a second type diffusely reflective surface can be used. The second-class diffuse reflectivity was obtained by giving unevenness to a surface having a mirror surface and dividing it into fine mirror surfaces facing different directions, and dispersing the directions of the divided fine surfaces (mirror surface). Refers to diffuse reflectivity. The unevenness of the surface of the second-class diffuse reflection has a three-dimensional average roughness of 0.1 to 2 μm, preferably 0.1 to 1.2 μm with respect to the center plane. The frequency of the surface irregularities is preferably 0.1 to 2000 cycles / mm for irregularities having a roughness of 0.1 μm or more, and more preferably 50 to 600 cycles / mm. For more information on such supports, see
It is described in JP-A-2-239244.

Suitable supports for the light-sensitive material are, for example, RD. 17643, page 28, 18716, page 647, right column, 648
It is described in the left column of the page and 879105, page 879.

In the light-sensitive material for photographing, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 23 μm or less, more preferably 20 μm or less, and 13 to 17 μm.
Is particularly preferable. The film swelling speed T _1/2 is preferably 5 to 15 seconds. T _1/2 is the time until the film thickness reaches 1/2 when 90% of the maximum swollen film thickness reached when the film is processed with a color developer at 30 ° C. for 3 minutes and 15 seconds is the saturated film thickness. It is defined as
T _1/2 can be adjusted by adding a hardening agent to gelatin as a binder or changing the aging condition after coating. The swelling rate is 150-350%
Is preferred. The swelling ratio can be calculated from the maximum swollen film thickness under the conditions described above by the formula: (maximum swollen film thickness-film thickness) / film thickness. The photosensitive material may be provided with a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer. This back layer preferably contains the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, and surface active agent. The swelling ratio of this back layer is preferably 150 to 500%.

As the light-sensitive material used in the present invention, the following materials can be preferably used. A light-sensitive material having a magnetic recording layer, which comprises magnetic particles (preferably Co-coated ferromagnetic iron oxide) dispersed in a binder, and is optically transparent. It is preferably provided on the entire surface. The magnetic particles may be treated with a coupling agent as described in JP-A-6-101632. As a binder,
Polymers described in JP-A No. 4-219569 and the like can be preferably used. The recording layer may be provided anywhere, but is preferably provided on the side opposite to the emulsion layer (back layer) with respect to the support. The upper layer of this recording layer is provided with a layer containing a slip agent,
It is preferable that the outermost layer on the photosensitive emulsion layer side of the support contains a matting agent. Further, the photosensitive material preferably contains an antistatic agent in order to impart antistatic properties even after development processing, and as the antistatic agent, a conductive metal oxide or an ionic polymer is preferred. . The antistatic agent is preferably used so that the electric resistance is 10 ¹² Ω · cm or less under the condition of 25 ° and 10% RH. Regarding the photosensitive material having a magnetic recording layer, U.S. Pat. Nos. 5,336,589, 5,250,404, 5,229,259 and 5,215,8 are disclosed.
74, EP 466130 A. The support used for the light-sensitive material is preferably a polyester support having an improved curl and having a thin layer. The thickness is preferably from 50 to 105 μm, and the material is preferably a polyethylene aromatic dicarboxylate-based polyester (preferably using benzenedicarboxylic acid, naphthalenedicarboxylic acid and ethylene glycol as main raw materials).
The glass transition temperature is preferably 50 to 200 degrees.
Further, as the surface treatment of the support, ultraviolet irradiation treatment, corona discharge treatment, glow discharge treatment and flame treatment are preferable. Further, it is preferable to perform heat treatment for 0.1 to 1500 hours in the range of 40 ° C. to the glass transition temperature of the support before or after applying the undercoat layer to the support and before coating the emulsion layer. In addition to the support, the light-sensitive material, the developing treatment, the cartridge, and the like are described in Published Technical Report No. 94-6023 (published by the Institute of Invention and Innovation, 1994).

[0109]

EXAMPLES The present invention will be described below in more detail with reference to examples, but the present invention is not limited thereto. Example 1 Preparation of Multi-Layer Color Photosensitive Material Each layer having the following composition was applied to prepare Sample 101 which is a multi-layer color photosensitive material. (Photosensitive layer composition) The main materials used for each layer are classified as follows; ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling point organic solvent ExY: Yellow coupler H: Gelatin Curing agent ExS: Sensitizing dye The numbers corresponding to the respective components indicate the coating amount expressed in units of g / m ² , and for silver halide, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer.

(Sample 101) First layer (antihalation layer) Black colloidal silver Silver 0.18 Gelatin 1.60 ExM-1 0.11 ExF-1 3.4 × 10 ^-3 ExF-2 (solid disperse dye) 0.03 ExF-3 (solid disperse dye) ) 0.04 HBS-1 0.16

Second layer (intermediate layer) ExC-2 0.055 UV-1 0.011 UV-2 0.030 UV-3 0.053 HBS-1 0.05 HBS-2 0.02 Polyethyl acrylate latex 8.1 × 10 ^-2 gelatin 1.75

Third Layer (Low Sensitivity Red Sensitive Emulsion Layer) Silver Iodobromide Emulsion A Silver 0.46 ExS-1 5.0 × 10 ^-4 ExS-2 1.8 × 10 ^-5 ExS-3 5.0 × 10 ^-4 ExC-1 0.16 ExC-3 0.045 ExC-5 0.0050 ExC-7 0.001 ExC-8 0.010 Cpd-2 0.005 HBS-1 0.090 Gelatin 0.87

Fourth layer (medium-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion D Silver 0.70 ExS-1 3.0 × 10 ^-4 ExS-2 1.2 × 10 ^-5 ExS-3 4.0 × 10 ^-4 ExC-1 0.22 ExC-2 0.055 ExC-5 0.007 ExC-8 0.009 Cpd-2 0.036 HBS-1 0.11 Gelatin 0.70

Fifth layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion E Silver 1.62 ExS-1 2.0 × 10 ^-4 ExS-2 1.0 × 10 ^-5 ExS-3 3.0 × 10 ^-4 ExC-1 0.133 ExC-3 0.040 ExC-6 0.040 ExC-8 0.014 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.10 Gelatin 0.85

Sixth layer (intermediate layer) Cpd-1 0.07 HBS-1 0.04 polyethyl acrylate latex 0.19 gelatin 2.30

Seventh Layer (Low Sensitivity Green Sensitive Emulsion Layer) Silver iodobromide Emulsion A Silver 0.24 Silver iodobromide Emulsion B Silver 0.10 Silver iodobromide Emulsion C Silver 0.14 ExS-4 4.0 × 10 ^-5 ExS-5 1.8 × 10 ^-4 ExS-6 6.5 × 10 ^-4 ExM-1 0.005 ExM-2 0.30 ExM-3 0.09 ExY-1 0.015 HBS-1 0.26 HBS-3 0.006 Gelatin 0.80

Eighth Layer (Medium-Sensitivity Green Sensitive Emulsion Layer) Silver Iodobromide Emulsion D Silver 0.94 ExS-4 2.0 × 10 ^-5 ExS-5 1.4 × 10 ^-4 ExS-6 5.4 × 10 ^-4 ExM-2 0.16 ExM-3 0.045 ExY-1 0.008 ExY-5 0.030 HBS-1 0.14 HBS-3 8.0 × 10 ^-3 Gelatin 0.90

Ninth layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion E Silver 1.29 ExS-4 3.7 × 10 ^-5 ExS-5 8.1 × 10 ^-5 ExS-6 3.2 × 10 ^-4 ExC-4 0.011 ExM-1 0.016 ExM-4 0.046 ExM-5 0.023 Cpd-3 0.050 HBS-1 0.20 HBS-2 0.08 Polyethyl acrylate latex 0.26 Gelatin 0.82

10th layer (yellow filter layer) Yellow colloidal silver Silver 0.010 Cpd-1 0.10 ExF-5 (solid disperse dye) 0.06 ExF-6 (solid disperse dye) 0.06 ExF-7 (oil soluble dye) 0.005 HBS-1 0.055 Gelatin 0.70

Eleventh layer (low sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion A Silver 0.25 Silver iodobromide emulsion C Silver 0.25 Silver iodobromide emulsion D Silver 0.10 ExS-7 8.0 × 10 ^-4 ExY-1 0.010 ExY-2 0.70 ExY-3 0.055 ExY-4 0.006 ExY-6 0.075 ExC-7 0.040 HBS-1 0.25 Gelatin 1.60

Twelfth layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion F Silver 1.30 ExS-7 3.0 × 10 ^-4 ExY-2 0.15 ExY-3 0.06 HBS-1 0.070 Gelatin 1.13

Thirteenth layer (first protective layer) UV-2 0.08 UV-3 0.11 UV-4 0.26 HBS-1 0.09 Gelatin 1.20

14th layer (second protective layer) Silver iodobromide emulsion G Silver 0.10 H-1 0.30 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter 1.7 μm) 0.10 B-3 0.10 S-1 0.20 Gelatin 1.75

Further, in order to improve the storability, processability, pressure resistance, antifungal / antibacterial property, antistatic property and coating property of each layer, W-1 to W-3, B-4 to B may be appropriately added. -6,
F-1 to F-17 and iron salts, lead salts, gold salts, platinum salts,
It contains iridium salt, palladium salt, and rhodium salt.

[0125]

[Table 1]

In Table 1, (1) Emulsions A to F were prepared according to the examples of JP-A-2-91938.
It is reduction-sensitized during grain preparation using thiourea dioxide and thiosulfonic acid. (2) Emulsions A to F were prepared according to the examples of JP-A-3-237450.
Gold sensitization, sulfur sensitization and selenium sensitization are performed in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate. (3) For the preparation of tabular grains, low molecular weight gelatin is used according to the examples of JP-A 1-158426. (4) Dislocation lines as described in JP-A-3-237450 are observed in the tabular grains by using a high voltage electron microscope.

Preparation of Dispersion of Organic Solid Disperse Dye ExF-2 shown below was dispersed by the following method. That is, water 2
1.7 ml and 3 ml of 5% aqueous solution of sodium p-octylphenoxyethoxyethane sulfonate and 0.5 g of 5% aqueous solution of p-octylphenoxypolyoxyethylene ether (polymerization degree 10) and 0.5 g were put into a 700 ml pot mill, and dye ExF- 5.0 g of 2 and 500 ml of zirconium oxide beads (diameter 1 mm) were added, and the contents were dispersed for 2 hours. For this dispersion, a BO type vibrating boat mill manufactured by Chuo Koki was used. After dispersion, take out the contents, 12.5%
Add to 8 g of gelatin aqueous solution, filter out beads,
A gelatin dispersion of the dye was obtained. The average particle size of the dye fine particles was 0.44 μm.

Similarly, solid dispersions of ExF-3, ExF-4 and ExF-6 were obtained. The average particle size of the fine dye particles is 0.24 μm, 0.45 μm, and 0.52 μm, respectively.
It was m. ExF-5 is a European patent application publication (EP)
The particles were dispersed by the microprecipitation dispersion method described in Example 1 of the specification of No. 0,549,489A. The average particle size was 0.06 μm.

[0129]

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[0130]

[Chemical 15]

[0131]

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[0132]

[Chemical 17]

[0133]

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[0134]

[Chemical 19]

[0135]

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[0136]

[Chemical 21]

[0137]

[Chemical formula 22]

[0138]

[Chemical formula 23]

[0139]

[Chemical formula 24]

[0140]

[Chemical 25]

[0141]

[Chemical formula 26]

[0142]

[Chemical 27]

[0143]

[Chemical 28]

[0144]

[Chemical 29]

[0145]

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[0146]

[Chemical 31]

[0147]

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(Treatment process) Process Treatment time Treatment temperature Replenishment amount * Tank capacity Color development 3 minutes 40.0 ° C 200 ml 2.0 liter Bleach 30 seconds 45.0 ° C 130 ml 0.7 liter Fixed (1) 30 seconds 45.0 ° C 100 ml 0.7 liter Settling (2) 30 seconds 45.0 ° C 70 ml 0.7 liters Washing (1) 15 seconds 45.0 ° C − 0.4 liters Washing (2) 15 seconds 45.0 ° C − 0.4 liters Washing (3) 15 seconds 45.0 ° C 400 ml 0.4 liters Dry 20 seconds 80 ℃ * Replenishment amount per 1 m ² of light-sensitive material (4 tank counter-current multi-stage cascade from washing (3) to fixing (2) (2 tank counter-current multi-stage from fixing (2) to fixing (1) cascade)

The composition of the processing liquid is shown below. (Color developer) Tank solution (g) Replenisher solution (g) Diethylenediaminetetraacetic acid 4.0 4.0 4,5-Dihydroxybenzene-1,3-disulfonate sodium 0.5 0.5 Sodium sulfite 3.9 6.5 Potassium carbonate 37.5 39.0 Potassium bromide 2.7 Iodine Potassium iodide 1.3 mg N-methylhydroxylamine hydrochloride 4.5 5.5 2-Methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulphate (p-5) 5.0 9.0 1.0 liter with addition of water 1.0 liter pH (prepared with potassium hydroxide and sulfuric acid) 10.05 10.25

(Bleaching solution) Tank solution (mol) Replenishing solution (mol) 1,3-Diaminopropanetetraacetic acid ferric salt ammonium monohydrate 0.33 0.50 ferric nitrate nonahydrate 0.30 4.5 ammonium bromide 0.80 1.20 Ammonium nitrate 0.20 0.30 Acetic acid 0.67 1.0 Add water 1.0 liter 1.0 liter pH [Prepared with ammonia water] 4.5 4.0

(Fixer) Common to tank and replenisher (g) Ammonium sulfite 28 Ammonium thiosulfate aqueous solution (700 g / l) 280 ml Imidazole 15 Ethylenediaminetetraacetic acid 15 Water-added 1.0 liter pH [Prepared with ammonia water and acetic acid] 5.8

(Washing water) Common to tank liquid and replenisher tap water is H type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH type anion exchange resin (Amberlite IR-400). To treat calcium and magnesium ions at a concentration of 3 mg / liter or less, and then add 20 mg / liter of sodium diisocyanurate dichloride and 0.15 g / liter of sodium sulfate to treat the mixture. Used water. The pH of this liquid was in the range of 6.5 to 7.5.

(Stabilizing Solution) Tank Solution and Replenishing Solution Common 1,2-Benzisothiazolin-3-one 0.1 Polyoxyethylene-p-monononyl 0.2 Phenyl ether (Average degree of polymerization 10) 1.0 liter pH by adding water , Adjusted with hydrochloric acid] 8.50

Image-wise exposure was given to Sample 101, and continuous processing was carried out until the replenishing amount of the bleach-fixing solution became 3 times the tank dose in the above processing step. The running treatment liquid thus obtained is referred to as treatment 201. Next, a similar color developing solution except that the color developing agent P-5 sulfate in the color developing solution is changed to equimolar amounts of the color developing agent for comparison shown in Table 2 and the color developing agent of the present invention. Was prepared, and each running treatment liquid (treatment 202
~ 210) was obtained. The speed of treatment was evaluated as follows. First, after subjecting the sample 101 to wedge exposure, the color development processing is changed from 1 minute to 3 minutes in steps of 10 seconds and processed using each running processing solution (processing 202 to 210) [running processing step (a )], And the optical densities of the yellow, magenta, and cyan images of the obtained sample were measured. Next, the sample 101 was exposed to the same wedge, and then processed in the comparative development processing step (b) described below, and the optical densities of the yellow, magenta, and cyan images were similarly measured. The density curve of the magenta image obtained in this comparative development processing step (b) was compared with each of the above-mentioned processing in steps of 10 seconds, and the color development time at which an equivalent or higher magenta density was obtained was determined and shown in Table 2. Using the samples for the time when the magenta density gave the same density, the degree of density decrease of the yellow and cyan images was evaluated next. The yellow and cyan densities of the respective samples were obtained at an exposure amount giving a magenta density of 2.0, and compared with the yellow and cyan densities obtained in the comparative development processing step (b), the density value (a negative value decreases the density, Table 2 shows the positive values for increasing the density. In addition, the fog density of yellow was measured using this sample,
Table 2 shows the difference from the fog density of yellow obtained in the comparative development processing step (b). Color developing agent for comparison

[0155]

[Chemical 33]

[0156]

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Comparative development processing step (b) (processing method) Process processing time Processing temperature Color development 3 minutes 15 seconds 38 ° C Bleaching 1 minute 00 seconds 38 ° C Bleaching fixing 3 minutes 15 seconds 38 ° C Washing (1) 40 seconds 35 ℃ Washing with water (2) 1 minute 00 seconds 35 ℃ Stabilization 40 seconds 38 ℃ Drying 1 minute 15 seconds 55 ℃

Next, the composition of the processing liquid will be described. (Color developer) (Unit g) Diethylenetriaminepentaacetic acid 1.0 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1. 5 mg hydroxylamine sulfate 2.4 4- [N-ethyl-N- (β-hydroxyethyl) amino] -2-methylaniline sulfate [P-5] 4.5 Water was added to 1.0 liter pH ( Adjust with potassium hydroxide and sulfuric acid) 10.05

(Bleaching Solution) (Unit g) Ethylenediaminetetraacetic acid ammonium ferric dihydrate 120.0 Ethylenediaminetetraacetic acid disodium salt 10.0 Ammonium bromide 100.0 Ammonium nitrate 10.0 Bleaching accelerator 0.005 mol _{(CH 3) 2 N-CH} 2 -CH 2 -SS-CH 2 -CH 2 -N (CH 3) 2 · 2HCl aqueous ammonia (27%) of 15.0 ml water was added to 1.0 l pH (ammonia Adjust with water and nitric acid) 6.3

(Bleach-fixing solution) (Unit: g) Ethylenediaminetetraacetic acid ammonium ferric dihydrate 50.0 Ethylenediaminetetraacetic acid disodium salt 5.0 Sodium sulfite 12.0 Ammonium thiosulfate aqueous solution (700 g / l) 240.0 Milliliter Ammonia water (27%) 6.0 ml Add water to 1.0 liter pH (adjust with ammonia water and acetic acid) 7.2

(Washing water) Tap water was used as an H-type strongly acidic cation exchange resin (Amberlite IR-produced by Rohm and Haas).
120B) and an OH type anion exchange resin (Amberlite IR-400) were passed through the column to treat calcium and magnesium ions at a concentration of 3 mg / liter or less, and then isocyanuric dichloride. Sodium 20 mg / liter and sodium sulfate 0.15 g / liter were added. The pH of this liquid was in the range of 6.5 to 7.5.

(Stabilizing Solution) (Unit: g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (Average degree of polymerization: 10) 0.2 Ethylenediaminetetraacetic acid disodium salt 0.05 1, 2,4-Triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 Water was added to 1.0 liter pH 8.5

[0163]

[Table 2]

From Table 2, it can be seen that the color developing agents of the present invention or Comparative Compounds 3 to 5 can obtain a magenta image density in a much faster development processing time than P-5 (Processing No. 201). Recognize. It is understood that the comparative compounds 3 to 5 have excellent quickness, but the yellow density and the cyan density are less likely to occur, and the yellow fog density is high.

With the color developing agent of the present invention, yellow density,
The color development of cyan density was greatly improved, and the fog density of yellow could be suppressed. That is, by using the developing agent of the present invention, it was possible to have a rapid processing speed, to secure the yellow and cyan densities, and at the same time to suppress the yellow fog density to a low level.

Example 2 After exposing the sample 101 in Example 1 to light, a developing treatment was carried out by the following processing method using the exemplified compound (D-10) of the present invention as a color developing agent in a color developing solution. However, it is preferable that a desired gradation can be obtained with a short color development time of 60 seconds and the fog density is low. Further, instead of the exemplified compound (D-10), the exemplified compound (D
-2), Exemplified Compound (D-11), Exemplified Compound (D-1)
Similar results could be obtained using 2).

Development processing step and processing solution composition Processing step Temperature Time Color development 45 ° C 60 seconds Bleach fixing 45 ° C 60 seconds Washing with water (1) 40 ° C for 15 seconds Washing with water (2) 40 ° C for 15 seconds Washing with water (3) 40 ° C for 15 seconds Stability 40 ℃ for 15 seconds Dry 80 ℃ for 30 seconds (Washing was carried out in 3 tank counter-current method from (3) to (1).)

Liquid composition (color developer) Tank liquid (g) Diethylenetriaminepentaacetic acid 4.0 1-Hydroxyethylidene-1,1diphosphonic acid 3.0 Sodium sulfite 4.0 Potassium carbonate 50.0 Potassium bromide 4.0 Potassium iodide 1.3 mg Hydroxylamine sulfate 4.0 Color developing agent (D-10) 19.2 Water is added to 1.0 liter pH (prepared with potassium hydroxide and sulfuric acid) 10.05 (bleach-fixing solution) (unit mol) Chelating agent represented by formula A 0.17 Ferric nitrate 9 Hydrate 0.15 Ammonium thiosulfate 1.25 Ammonium sulfite 0.10 Metacarboxybenzenesulfinic acid 0.05 Add water 1.0 liter pH (prepared with acetic acid and ammonia) 5.8 (Wash water) Tap water for H-type strongly acidic cation exchange resin (Rohm and Haas Company) Amberlite IR-120B made)
And OH type anion exchange resin (the same Amberlite IR-
400) was passed through a mixed bed type column to treat calcium and magnesium ions at a concentration of 3 mg / liter or less, followed by 20 mg of sodium diisocyanurate dichloride.
/ L and water treated with the addition of 0.15 g / L of sodium sulfate were used. The pH of this solution is 6.5
It was in the range of 7.5. (Stabilizer) Tank liquid (g) 1,2-Benzisothiazolin-3-one 0.1 Polyoxyethylene-p-monononylphenyl ether (Average degree of polymerization 10) 0.2 Water added 1.0 liter pH [Ammonia water, hydrochloric acid Adjustment] 8.50

[0169]

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Example 3 After exposing the sample 101 in Example 1, the processing number 201 was used.
To 210 and D-2 as a color developing agent in the color developing solution.
2 and D-41 were processed in the same manner, and the magenta density was 2.
When the image fastness of the sample given 0 was examined, the compound of the present invention had good image fastness.

Example 4 In Example 3, Sample 301 described in JP-A-5-188550, a color developing agent (D) of the present invention (D) was used in an equimolar amount of the color developing agent in the color developing solution described in the publication. -2), (D-
10), (D-11), and (D-12) except that the same processing solution was prepared and exposed and developed, the developing time can be shortened, the fog density is low, and the magenta density is low. The difference between the yellow density and the cyan density was small, which was preferable.

[0172]

By using the color developing agent of the present invention, it is suitable for rapid processing, has a sufficient image density for all of yellow, magenta and cyan, has a low fog density, and has good image fastness. Images can be obtained.

Claims (3)

[Claims] 1. A color developing agent represented by the following general formula (D). General formula (D) In the formula, R ¹ and R ² each represent an alkyl group, and R ³ represents a substituent. n represents an integer of 0 to 2. Z represents a nonmetallic atom group forming a 5- or 6-membered aromatic ring containing 1 to 3 carbon atoms. 2. A color photographic processing composition comprising at least one color-developing agent according to claim 1. 3. A silver halide color photographic light-sensitive material imagewise exposed to at least one of the color developing agents according to claim 1.
A method for forming a color image, which comprises developing with a treatment liquid containing a seed.